Compositions comprising tetrafluoropropene and methods of use thereof

ABSTRACT

The present invention relates to a composition comprising HFO-1234yf, or trans-HFO-1234ze, or a mixture thereof; HFC-32; and HFC-152a, HFO-1243zf, or a mixture thereof, wherein said composition is selected from the group consisting of:
     (I) a first composition, wherein said HFO-1234yf or trans-HFO-1234ze or a mixture thereof is at least 56 weight percent of said first composition;   (II) a second composition, wherein said HFC-32 is at most 29 weight percent of said second composition;   (III) a third composition, wherein said HFC-152 a  is at least 56 weight percent said third composition;   (IV) a fourth composition, wherein said HFC-32 is at least 56 weight percent of said fourth composition;   (V) a fifth composition comprising trans-HFO-1234ze, HFC-32, and HFC-152a, HFO-1243zf, or a mixture thereof; and   (VI) a sixth composition, wherein said HFO-1243zf or mixture thereof with HFC-152a is at most 20 weight percent of said sixth composition.

BACKGROUND 1. Field of the Disclosure

The present disclosure relates to compositions comprising2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,3,3,3-tetrafluoropropene(trans-HFO-1234ze) or a mixture thereof; difluoromethane (HFC-32); and1,1, difluoroethane (HFC-152a), 3,3,3-trifluoropropene (HFO-1243zf) ormixture thereof.

The compositions of the present invention are useful in processes forproducing cooling or heat, as heat transfer fluids, foam blowing agents,aerosol propellants, and as power cycle working fluids.

2. Description of Related Art

The refrigeration industry has been working for the past few decades tofind replacement refrigerants for the ozone-depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCsand the HCFCs are being phased out as a result of the Montreal Protocol.The solution for most refrigerant producers has been thecommercialization of hydrofluorocarbon (HFC) refrigerants. For example,the new HFC refrigerants, HFC-134a being the most widely used at thistime, have zero ozone depletion potential and thus are not affected bythe current regulatory phase out as a result of the Montreal Protocol.

However, further environmental regulations may ultimately cause globalphase out of certain HFC refrigerants. Currently, the industry facesregulations relating to global warming potential (GWP) for refrigerantsused in mobile air-conditioning. Should the regulations be more broadlyapplied in the future, for instance for stationary air conditioning andrefrigeration systems, an even greater need will be felt forrefrigerants that can be used in all areas of the refrigeration andair-conditioning industry. Uncertainty as to the ultimate regulatoryrequirements relative to GWP, have forced the industry to considermultiple candidate compounds and mixtures.

Currently proposed replacement refrigerants for HFC refrigerants andrefrigerant blends include, for example, pure hydrocarbons such asbutane or propane, or “natural” refrigerants such as CO2. However, thesesuggested replacements have problems including toxicity, flammability,low energy efficiency, or require major equipment design modifications.Similarly, new replacements are being proposed also for R-22, R-134a,R-404A, and R-407C among others. Uncertainty as to what regulatoryrequirements relative to GWP will ultimately be adopted have forced theindustry to consider multiple candidate compounds and mixtures thatbalance the need for low GWP, non-flammability or low flammability, andexisting system performance parameters.

BRIEF SUMMARY

The present invention discloses low-GWP compositions as replacements forcurrently used refrigerants, including but not limited to existingrefrigerants (see definition infra) such as R-407C (ASHRAE designationfor a blend of 50 weight percent R125 and 50 weight percent R32), R-404A(ASHRAE designation for a blend of 44 weight percent R125, 52 weightpercent R143a (1,1,1-trifluoroethane), and 4.0 weight percent R-134a),and R-22.

Often replacement refrigerants are most useful if capable of being usedin the original refrigeration equipment designed for a differentrefrigerant. The compositions as disclosed herein may be useful asreplacements for existing refrigerants (see definition infra) such asR-407C, R-404A, R-134a, and R-22 in equipment designed for existingrefrigerants (see definition infra) such as R-407C, R-404A, R-134a, andR-22, respectively, with some system modifications. Further, thecompositions as disclosed herein comprising HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; HFC-32; HFC-152a, HFO-1243zf ormixture thereof; and optionally R-134a may be useful as replacements forexisting refrigerants (see definition infra) such as R-404A, R-407C,R-134a, and R-22 in equipment specifically modified for or producedentirely for these new compositions comprising HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; HFC-32; HFC-152a, HFO-1243zf ormixture thereof; and optionally R-134a.

In one embodiment, the present invention relates to a compositioncomprising HFO-1234yf or trans-HFO-1234ze or a mixture thereof;difluoromethane (HFC-32); and 1,1-difluoroethane (HFC-152a),3,3,3-trifluoropropene (HFO-1243zf) or mixture thereof; wherein saidcomposition is selected from the group consisting of:

-   (I) a first composition, wherein said HFO-1234yf or trans-HFO-1234ze    or a mixture thereof is at least 56weight percent of the total    weight of said first composition;-   (II) a second composition, wherein said HFC-32 is at most 29 weight    percent of the total weight of said second composition;-   (III) a third composition, wherein said HFC-152a, HFO-1243zf or    mixture thereof is at least 56 weight percent of the total weight of    said third composition;-   (IV) a fourth composition, wherein said HFC-32 is at least 56 weight    percent of the total weight of said fourth composition;-   (V) a fifth composition comprising trans-HFO-1234ze; HFC-32; and    HFC-152a, HFO-1243zf or mixture thereof; and-   (VI) a sixth composition, wherein said HFO-1243zf or mixture thereof    with HFC-152a is at most 20 weight percent of the total weight of    said sixth composition.

This invention also relates to the above compositions wherein saidcompositions have a cooling capacity in the range of from about 75% toabout 130% of at least one compound selected from the group of existingrefrigerants (see definition infra) such as R-22, HFC-134a, R-404A, andR-407C.

This invention also relates to the above compositions consistingessentially of HFO-1234ze; HFC-32; and HFC-152a, HFO-1243zf or mixturethereof, wherein the HFC-152a, HFO-1243zf or mixture thereof is presentat no more than about 15 weight percent of the total composition.

This invention also relates to a composition comprising HFO-1234yf ortrans-HFO-1234ze or a mixture thereof ; HFC-32; and HFC-152a, HFO-1243zfor mixture thereof; wherein the HFC-152a, HFO-1243zf or mixture thereofis in the range of from about 14 weight percent to about 16 weightpercent, and wherein said composition has a cooling capacity in therange of from about 75% to about 130% of at least one compound selectedfrom the group existing refrigerants (see definition infra) such asR-22, HFC-134a, R-404A, and R-407C.

In another embodiment, the compositions described supra further compriseat least one other saturated HFC, described infra, in the range of fromabout 0 weight percent (not included) to about 10 weight percent.

Another embodiment of the present invention relates to compositionsrecited above, wherein the GWP of said composition is less than the GWPof at least one compound selected from the group existing refrigerants(see definition infra) such as R-134a, R-22, R-407C, and R-404A.

The present invention also relates to a process to produce coolingcomprising condensing the above-described compositions and thereafterevaporating said compositions in the vicinity of a body to be cooled.The present invention also relates to a process to produce heatcomprising condensing compositions described above in the vicinity of abody to be heated and thereafter evaporating said compositions.

In yet another embodiment, this invention relates to a method forreplacing existing refrigerants (see definition infra) such as R-22,R-404A, R-407C, or R-134a in a system designed to use R-22, R-404A,R-407C, or R-134a, respectively, wherein said method comprises providingcompositions described above to said system.

This invention also relates to a refrigeration system, air-conditioningsystem, a stationary air conditioning apparatus, a stationaryrefrigeration system, an automotive air conditioner, or a heat pumpcontaining compositions described above. The invention also relates to aprocess for using compositions described above as a power cycle workingfluids.

This invention also relates to a composition comprising HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a, HFO-1243zfor mixture thereof; wherein the HFC-152a, HFO-1243zf or mixture thereofis in the range of from about 14 weight percent to about 16 weightpercent, and wherein said composition has a cooling capacity in therange of from about 75% to about 130% of at least one compound selectedfrom the group of existing refrigerants (see definition infra) such asR-22, HFC-134a, R-404A, and R-407C.

Also disclosed herein are methods of producing cooling and heating,methods for replacing existing refrigerants such as R-134a, R410A andR-404A, and air conditioning and refrigeration apparatus containingcompositions comprising HFO-1234yf or trans-HFO-1234ze or a mixturethereof; HFC-32; and HFC-152a, HFO-1243zf or mixture thereof.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 describes Estimated Burning Velocity ofHFO-1234yf/HFC-32/HFC-152a mixture as a function of theHFO-1234yf/HFC-152a ratio.

DETAILED DESCRIPTION

Before addressing details of embodiments described below, some terms aredefined or clarified.

Definitions

As used herein, the term heat transfer composition means a compositionused to carry heat from a heat source to a heat sink.

A heat source is defined as any space, location, object or body fromwhich it is desirable to add, transfer, move or remove heat. Examples ofheat sources are spaces (open or enclosed) requiring refrigeration orcooling, such as refrigerator or freezer cases in a supermarket,building spaces requiring air conditioning, industrial water chillers orthe passenger compartment of an automobile requiring air conditioning.In some embodiments, the heat transfer composition may remain in aconstant state throughout the transfer process (i.e., not evaporate orcondense). In other embodiments, evaporative cooling processes mayutilize heat transfer compositions as well.

A heat sink is defined as any space, location, object or body capable ofabsorbing heat. A vapor compression refrigeration system is one exampleof such a heat sink.

A heat transfer system is the system (or apparatus) used to produce aheating or cooling effect in a particular space. A heat transfer systemmay be a mobile system or a stationary system.

Examples of heat transfer systems include but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,mobile refrigerators, mobile air conditioning units, dehumidifiers, andcombinations thereof.

As used herein, mobile heat transfer system refers to any refrigeration,air conditioner or heating apparatus incorporated into a transportationunit for the road, rail, sea or air. In addition, mobile refrigerationor air conditioner units, include those apparatus that are independentof any moving carrier and are known as “intermodal” systems. Suchintermodal systems include “container’ (combined sea/land transport) aswell as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems that arefixed in place during operation. A stationary heat transfer system maybe associated within or attached to buildings of any variety or may bestand-alone devices located out of doors, such as a soft drink vendingmachine. These stationary applications may be stationary airconditioning and heat pumps, including but not limited to chillers, hightemperature heat pumps, residential, commercial or industrial airconditioning systems (including residential heat pumps), and includingwindow, ductless, ducted, packaged terminal, and those exterior butconnected to the building such as rooftop systems. In stationaryrefrigeration applications, the disclosed compositions may be useful inequipment including commercial, industrial or residential refrigeratorsand freezers, ice machines, self-contained coolers and freezers, floodedevaporator chillers, direct expansion chillers, walk-in and reach-incoolers and freezers, and combination systems. In some embodiments, thedisclosed compositions may be used in supermarket refrigeration systems.Additionally, stationary applications may utilize a secondary loopsystem that uses a primary refrigerant to produce cooling in onelocation that is transferred to a remote location via a secondary heattransfer fluid.

Refrigeration capacity (also referred to as cooling capacity) is a termwhich defines the change in enthalpy of a refrigerant in an evaporatorper pound of refrigerant circulated, or the heat removed by therefrigerant in the evaporator per unit volume of refrigerant vaporexiting the evaporator (volumetric capacity). The refrigeration capacityis a measure of the ability of a refrigerant or heat transfercomposition to produce cooling. Therefore, the higher the capacity, thegreater the cooling that is produced. Cooling rate refers to the heatremoved by the refrigerant in the evaporator per unit time.

Coefficient of performance (COP) is the amount of heat removed dividedby the required energy input to operate the cycle. The higher the COP,the higher is the energy efficiency. COP is directly related to theenergy efficiency ratio (EER) that is the efficiency rating forrefrigeration or air conditioning equipment at a specific set ofinternal and external temperatures.

The term “subcooling” refers to the reduction of the temperature of aliquid below that liquid's saturation point for a given pressure. Thesaturation point is the temperature at which the vapor is completelycondensed to a liquid, but subcooling continues to cool the liquid to alower temperature liquid at the given pressure. By cooling a liquidbelow the saturation temperature (or bubble point temperature), the netrefrigeration capacity can be increased. Subcooling thereby improvesrefrigeration capacity and energy efficiency of a system. Subcool amountis the amount of cooling below the saturation temperature (in degrees).

Superheat is a term that defines how far above its saturation vaportemperature (the temperature at which, if the composition is cooled, thefirst drop of liquid is formed, also referred to as the “dew point”) avapor composition is heated.

Temperature glide (sometimes referred to simply as “glide”) is theabsolute value of the difference between the starting and endingtemperatures of a phase-change process by a refrigerant within acomponent of a refrigerant system, exclusive of any subcooling orsuperheating. This term may be used to describe condensation orevaporation of a near azeotrope or non-azeotropic composition. Whenreferring to the temperature glide of a refrigeration, air conditioningor heat pump system, it is common to provide the average temperatureglide being the average of the temperature glide in the evaporator andthe temperature glide in the condenser.

By azeotropic composition is meant a constant-boiling mixture of two ormore substances that behave as a single substance. One way tocharacterize an azeotropic composition is that the vapor produced bypartial evaporation or distillation of the liquid has the samecomposition as the liquid from which it is evaporated or distilled,i.e., the mixture distills/refluxes without compositional change.Constant-boiling compositions are characterized as azeotropic becausethey exhibit either a maximum or minimum boiling point, as compared withthat of the non-azeotropic mixture of the same compounds. An azeotropiccomposition will not fractionate within a refrigeration or airconditioning system during operation. Additionally, an azeotropiccomposition will not fractionate upon leakage from a refrigeration orair conditioning system.

A near-azeotropic composition (also commonly referred to as an“azeotrope-like composition”) is a substantially constant boiling liquidadmixture of two or more substances that behaves essentially as a singlesubstance. One way to characterize a near-azeotropic composition is thatthe vapor produced by partial evaporation or distillation of the liquidhas substantially the same composition as the liquid from which it wasevaporated or distilled, that is, the admixture distills/refluxeswithout substantial composition change. Another way to characterize anear-azeotropic composition is that the bubble point vapor pressure andthe dew point vapor pressure of the composition at a particulartemperature are substantially the same. Herein, a composition isnear-azeotropic if, after 50 weight percent of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed isless than about 10 percent.

A non-azeotropic composition is a mixture of two or more substances thatbehaves as a simple mixture rather than a single substance. One way tocharacterize a non-azeotropic composition is that the vapor produced bypartial evaporation or distillation of the liquid has a substantiallydifferent composition as the liquid from which it was evaporated ordistilled, that is, the admixture distills/refluxes with substantialcomposition change. Another way to characterize a non-azeotropiccomposition is that the bubble point vapor pressure and the dew pointvapor pressure of the composition at a particular temperature aresubstantially different. Herein, a composition is non-azeotropic if,after 50 weight percent of the composition is removed, such as byevaporation or boiling off, the difference in vapor pressure between theoriginal composition and the composition remaining after 50 weightpercent of the original composition has been removed is greater thanabout 10 percent.

As used herein, the term “lubricant” means any material added to acomposition or a compressor (and in contact with any heat transfercomposition in use within any heat transfer system) that provideslubrication to the compressor to aid in preventing parts from seizing.

As used herein, compatibilizers are compounds which improve solubilityof the hydrofluorocarbon of the disclosed compositions in heat transfersystem lubricants. In some embodiments, the compatibilizers improve oilreturn to the compressor. In some embodiments, the composition is usedwith a system lubricant to reduce oil-rich phase viscosity.

As used herein, oil-return refers to the ability of a heat transfercomposition to carry lubricant through a heat transfer system and returnit to the compressor. That is, in use, it is not uncommon for someportion of the compressor lubricant to be carried away by the heattransfer composition from the compressor into the other portions of thesystem. In such systems, if the lubricant is not efficiently returned tothe compressor, the compressor will eventually fail due to lack oflubrication.

As used herein, “ultra-violet” dye is defined as a UV fluorescent orphosphorescent composition that absorbs light in the ultra-violet or“near” ultra-violet region of the electromagnetic spectrum. Thefluorescence produced by the UV fluorescent dye under illumination by aUV light that emits at least some radiation with a wavelength in therange of from 10 nanometers to about 775 nanometers may be detected.

Flammability is a term used to mean the ability of a composition toignite and/or propagate a flame. For refrigerants and other heattransfer compositions, the lower flammability limit (“LFL”) is theminimum concentration of the heat transfer composition in air that iscapable of propagating a flame through a homogeneous mixture of thecomposition and air under test conditions specified in ASTM (AmericanSociety of Testing and Materials) E681. The upper flammability limit(“UFL”) is the maximum concentration of the heat transfer composition inair that is capable of propagating a flame through a homogeneous mixtureof the composition and air under the same test conditions. In order tobe classified by ASHRAE (American Society of Heating, Refrigerating andAir-Conditioning Engineers) as non-flammable, a refrigerant must benon-flammable under the conditions of ASTM E681 as formulated in boththe liquid and vapor phase as well as non-flammable in both the liquidand vapor phases that result during leakage scenarios.

Global warming potential (GWP) is an index for estimating relativeglobal warming contribution due to atmospheric emission of a kilogram ofa particular greenhouse gas compared to emission of a kilogram of carbondioxide. GWP can be calculated for different time horizons showing theeffect of atmospheric lifetime for a given gas. The GWP for the 100 yeartime horizon is commonly the value referenced. For mixtures, a weightedaverage can be calculated based on the individual GWPs for eachcomponent.

Ozone depletion potential (ODP) is a number that refers to the amount ofozone depletion caused by a substance. The ODP is the ratio of theimpact on ozone of a chemical compared to the impact of a similar massof CFC-11 (fluorotrichloromethane). Thus, the ODP of CFC-11 is definedto be 1.0. Other CFCs and HCFCs have ODPs that range from 0.01 to 1.0.HFCs have zero ODP because they do not contain chlorine.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a composition,process, method, article, or apparatus that comprises a list of elementsis not necessarily limited to only those elements but may include otherelements not expressly listed or inherent to such composition, process,method, article, or apparatus. Further, unless expressly stated to thecontrary, “or” refers to an inclusive or and not to an exclusive or. Forexample, a condition A or B is satisfied by any one of the following: Ais true (or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method or apparatus that includes materials, steps,features, components, or elements, in addition to those literallydisclosed provided that these additional included materials, steps,features, components, or elements do materially affect the basic andnovel characteristic(s) of the claimed invention. The term ‘consistingessentially of’ occupies a middle ground between “comprising” and‘consisting of’.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the disclosed compositions,suitable methods and materials are described below. All publications,patent applications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

Compositions

In one embodiment, the present invention relates to compositionscomprising three components, that is, 2,3,3,3-tetrafluoropropene(HFO-1234yf), difluoromethane (HFC-32), and 1,1-difluoroethane(HFC-152a), 3,3,3-trifluoropropene (HFO-1243zf) or mixture thereof. Wenote that in all exemplary embodiments disclosed herein, HFO-1234yf isused only as an example. In place of HFO-1234yf, trans-HFO-1234ze or itsmixture with HFO-1234yf can also be used. Therefore, it is to beunderstood that in all examples infra and supra, HFO-1234yf also impliestrans-HFO-1234ze and its mixture with HFO-1234yf are also implicated forthe purposes of this invention, its disclosure, its patentability, andits claim scope, unless indicated otherwise. Thus, generally speaking, areference to HFO-1234yf includes the trans-HFO-1234ze and its mixturewith HFO-1234yf.

In another embodiment, the present invention relates to compositionscomprising four components, that is, HFO-1234yf or trans-HFO-1234ze or amixture thereof, HFC-32, HFC-152a, and at least one otherhydrofluorocarbon comprising saturated compound comprising carbon,hydrogen, and fluorine.

A mixture of HFO-1234yf and trans-HFO-1234ze comprises from about 1weight percent to about 99 weight percent of HFO-1234yf and from about 1weight percent to about 99 weight percent of trans-HFO-1234ze. In otherembodiments, the HFO-1234yf is selected from one of the followingcontents expressed in percentage of the total weight of the twocomponents:

-   -   about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,        18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33,        34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49,        50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65,        66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,        82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97,        98, and 99 weight percent.

In other embodiments, the trans-HFO-1234ze is selected from one of thefollowing contents expressed in percentage of the total weight of thetwo components:

-   -   about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,        18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33,        34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49,        50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65,        66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,        82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97,        98, and 99 weight percent.

2,3,3,3-tetrafluoropropene may also be referred to as HFO-1234yf,HFC-1234yf, or R1234yf. HFO-1234yf is available commercially or may bemade by methods known in the art, such as by dehydrofluorination1,1,1,2,3-pentafluoropropane (HFC-245eb) or 1,1,1,2,2-pentafluoropropane(HFC-245cb). HFO-1234yf and trans-HFO-1234ze are non-ozone depletingcompounds with low global warming potential. HFO-1234yf flammability isclassified as 2L or low flammability according to ASHRAE Standard34-2010.

Trans-1,3,3,3-tetrafluoropropene may also be referred to astrans-HFO-1234ze or trans-HFC-1234ze. Trans-HFO-1234ze may be made bymethods known in the art such as by dehydrofluorination of1,1,1,2,3-pentafluoropropane (HFC-245eb) or 1,1,1,3,3-pentafluoropropane(HFC-245fa).

Difluoromethane (HFC-32 or R32) is commercially available or may be madeby methods known in the art, such as by dechlorofluorination ofmethylene chloride. HFC-32 is a non-ozone depleting compound with lowglobal warming potential. HFC-32 flammability is classified as 2L or lowflammability according to ASHRAE Standard 34-2010.

1,1-Difluoroethane may also be referred to as HFC-152a or R152a.HFC-152a is commercially available or may be made by methods known inthe art such by reaction of vinyl chloride with hydrogen fluoride in thepresence of a catalyst. HFC-152a is non-ozone depleting compound withlow global warming potential. HFC-152a flammability is classified as 2or moderate flammability according to ASHRAE Standard 34-2010.

3,3,3-Trifluoropropene may also be referred to as HFO-1243zf,HFC-1243zf, or TFP. HFO-1243zf is available commercially or may be madeby methods known in the art such as by hydrogenation of1,3,3,3-tetrafluoropropene to give 1,1,1,3-tetrafluoropropane and thendehydrofluorination of 1,1,1,3-tetrafluoropropane as described in U.S.Pat. No. 5,986,151. It has been found that the compositions of thepresent invention are useful in processes for producing cooling or heat,as heat transfer fluids, foam blowing agents, and aerosol propellants.But that at the same time, these compositions will help reducerefrigerant costs while maintaining cooling capacity and energyefficiency with no substantial flammability increases. Generally, theflammability of the preferred embodiments of the present invention is atthe 2L level and certainly no greater than 2.

Both HFO-1234yf or trans-HFO-1234ze or a mixture thereof, and HFC-32 arebeing considered as low GWP replacements for certain refrigerants andrefrigerant mixtures that have relatively high GWP. In particular,R-404A has a GWP of 3922 and will be in need of replacement. Further,R507 (ASHRAE designation for a mixture containing 50 wt % HFC-125 and 50wt % HFC-143a), which has virtually identical properties to R-404A andcan therefore be used in many R-404A systems, has a GWP equal to 3985,and therefore will be in need of replacement as well. Similarly, R-22and R-407C have a GWP of 1810 and 1774 respectively. Also HFC-134a(tetrafluoroethane, in particular 1,1,1,2-tetrafluoroethane) iscurrently used as a refrigerant in many applications, has a GWP of 1430and is in need of replacement.

This invention generally relates to compositions comprising HFC-152a inaddition to the HFO-1234yf or trans-HFO-1234ze or a mixture thereof, andHFC-32 components. It has been found that in one embodiment of theinvention, a three-component system as described herein can reduce theoverall GWP to below 300, while maintaining at least about 75% of thecooling capacity relative to existing refrigerants (see definitioninfra) such as R-134a, R-22, R-407C, and R-404A.

In some embodiments of the present invention, the compositions mayinclude at least one other hydrofluorocarbon comprising a saturatedcompound comprising carbon, hydrogen, and fluorine (hereinafter“saturated HFC”) include hydrofluorocarbons having 1-7 carbon atoms andhaving a normal boiling point of from about −90° C. to about 80° C. Suchsaturated HFCs are commercial products available from a number ofsources such as E. I. du Pont de Nemours & Co., Fluoroproducts,Wilmington, Del., 19898, USA, or may be prepared by methods known in theart. Representative saturated HFC compounds include but are not limitedto fluoromethane (CH₃F, HFC-41), trifluoromethane (CHF₃, HFC-23),pentafluoroethane (CF₃CHF₂, HFC-125), 1,1,2,2-tetrafluoroethane(CHF₂CHF₂, HFC-134), 1,1,1,2-tetrafluoroethane (CF₃CH₂F, HFC-134a),1,1,1-trifluoroethane (CF₃CH₃, HFC-143a), fluoroethane (HFC-161,CH₃CH₂F), 1,1,1,2,2,3,3-heptafluoropropane (CF₃CF₂CHF₂, HFC-227ca),1,1,1,2,3,3,3-heptafluoropropane (CF₃CHFCF₃, HFC-227ea),1,1,2,2,3,3,-hexafluoropropane (CHF₂CF₂CHF₂, HFC-236ca),1,1,1,2,2,3-hexafluoropropane (CF₃CF₃CH₂F, HFC-236cb),1,1,1,2,3,3-hexafluoropropane (CF₃CHFCHF₂, HFC-236ea),1,1,1,3,3,3-hexafluoropropane (CF₃CH₂CF₃, HFC-236fa),1,1,2,2,3-pentafluoropropane (CHF₂CF₂CH₂F, HFC-245ca),1,1,1,2,2-pentafluoropropane (CF₃CF₂CH₃, HFC-245cb),1,1,2,3,3-pentafluoropropane (CHF₂CHFCHF₂, HFC-245ea),1,1,1,2,3-pentafluoropropane (CF₃CHFCH₂F, HFC-245eb),1,1,1,3,3-pentafluoropropane (CF₃CH₂CHF₂, HFC-245fa),1,2,2,3-tetrafluoropropane (CH₂FCF₂CH₂F, HFC-254ca),1,1,2,2-tetrafluoropropane (CHF₂CF₂CH₃, HFC-254cb),1,1,2,3-tetrafluoropropane (CHF₂CHFCH₂F, HFC-254ea),1,1,1,2-tetrafluoropropane (CF₃CHFCH₃, HFC-254eb),1,1,3,3-tetrafluoropropane (CHF₂CH₂CHF₂, HFC-254fa),1,1,1,3-tetrafluoropropane (CF₃CH₂CH₂F, HFC-254fb),1,1,1-trifluoropropane (CF₃CH₂CH₃, HFC-263fb), 2,2-difluoropropane(CH₃CF₂CH₃, HFC-272ca), 1,2-difluoropropane (CH₂FCHFCH₃, HFC-272ea),1,3-difluoropropane (CH₂FCH₂CH₂F, HFC-272fa), 1,1-difluoropropane(CHF₂CH₂CH₃, HFC-272fb), 2-fluoropropane (CH₃CHFCH₃, HFC-281ea),1-fluoropropane (CH₂FCH₂CH₃, HFC-281fa),1,1,2,2,3,3,4,4-octafluorobutane (CHF₂CF₂CF₂CHF₂, HFC-338pcc),1,1,1,2,2,4,4,4-octafluorobutane (CF₃CH₂CF₂CF₃, HFC-338mf),1,1,1,3,3-pentafluorobutane (CF₃CH₂CHF₂, HFC-365mfc),1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF₃CHFCHFCF₂CF₃, HFC-43-10mee),and 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane(CF₃CF₂CHFCHFCF₂CF₂CF₃, HFC-63-14mee).

Of particular utility as the other saturated HFC compounds would bethose non-flammable fluorocarbon refrigerants including HFC-134,HFC-134a, HFC-125 (pentafluoroethane), HFC-23 (trifluoromethane),HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-227ea(1,1,1,2,3,3,3-heptafluoropropane), and CF₃I. All of these could beadded to improve flammability characteristics due to their non-flammablenature.

Exemplary Embodiment 1

In a first exemplary embodiment of the present invention, thecomposition comprises three components: (A) HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; (B) HFC-32; and (C) HFC-152a,HFO-1243zf or a mixture thereof; wherein said HFO-1234yf ortrans-HFO-1234ze or a mixture thereof is greater than about 56 weightpercent.

For the composition of this embodiment, it is to be understood that theHFO-1234yf or trans-HFO-1234ze or a mixture thereof content is greaterthan about 56 weight percent by weight of the total composition, but atthe same time, some amount of HFC-32 and some amount of HFC-152a arealways present in the compositions of this embodiment.

For the compositions of this embodiment:

-   (A1) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content can    be about 56%, ₅₇%_(, 58)%_(,) 59%, 60%, 81%, 62%, 63%, 64%, 65%,    66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%,    79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%,    92%, 93%, 94%, 95%, 96%, 97%, 98%, or about 99% by weight of the    composition;-   (B1) HFC-32 can be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%,    11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%,    24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%,    37%, 38%, 39%, 40%, 41%, 42%, or about 43% by weight of the    composition; and-   (C1) HFC-152a or HFO-1243zf or a mixture thereof content can be    about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%,    15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%,    28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%,    41%, 42%, or about 43% by weight of the composition.    Also, for the compositions of this embodiment:-   (A1′) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content    can also be a weight percent number that is in between the specific    weight percent numbers cited supra. For example, HFO-1234yf or    trans-HFO-1234ze or a mixture thereof can be about 56.5%, 57.5%,    58.5%, 59.5%, 60.5%, 61.5%, 62.5%, 63.5%, 64.5%, 65.5%, 66.5%,    67.5%, 68.5%, 69.5%, 70.5%, 71.5%, 72.5%, 73.5%, 74.5%, 75.5%,    76.5%, 77.5%, 78.5%, 79.5%, 80.5%, 81.5%, 82.5%, 83.5%, 84.5%,    85.5%, 86.5%, 87.5%, 88.5%, 89.5%, 90.5%, 91.5%, 92.5%, 93.5%,    94.5%, 95.5%, 96.5%, 97.5%, 98.5% by weight of the composition;-   (B1′) HFC-32 content can also be a weight percent number that is in    between the specific weight percent numbers cited supra. For    example, HFC-32 can be about 0.5%, 1.5%, 2.5%, 3.5%, 4.5%, 5.5%,    6.5%, 7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%, 13.5%, 14.5%, 15.5%,    16.5, 17.%5, 18.5%, 19.5%, 20.5%, 21.5%, 22.5%, 23.5%, 24.5%, 25.5%,    26.5%, 27.5%, 28.5%, 29.5%, 30.5%, 31.5%, 32.5%, 33.5%, 34.5%,    35.5%, 36.5%, 37.5%, 38%, 39.5%, 40.5%, 41.5%, 42.5%, or about 43.5%    by weight of the composition; and-   (C1′) HFC-152a or HFO-1243zf or a mixture thereof content can also    be a weight percent number that is in between the specific weight    percent numbers cited supra. For example, HFC-152a can be about    0.5%, 1.5%, 2.5%, 3.5%, 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, 10.5%,    11.5%, 12.5%, 13.5%, 14.5%, 15.5%, 16.5%, 17.5%, 18.5%, 19.5%,    20.5%, 21.5%, 22.5%, 23.5%, 24.5%, 25.5%, 26.5%, 27.5%, 28.5%,    29.5%, 30.5%, 31.5%, 32.5%, 33.5%, 34.5%, 35.5%, 36.5%, 37.5%, 38%,    39.5%, 40.5%, 41.5%, 42.5%, or about 43.5% by weight of the    composition.-   (D1) In an alternative embodiment, at least one saturated HFC, as    described supra, may also be included in the compositions described    above. The weight percent of said at least one saturated HFC to the    total weight of the composition can be in the range of from about 0    weight percent to about 10 weight percent. The weight percent of    said at least one saturated HFC in the composition can be about    0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,    7%, 7.5%, 8%, 8.5%, 9%, 9.5%, and 10%.

Similarly, other numbers in between the integer numbers supra, forexample, 56.1, 56.2, 56.3 and the like can also be included for thecontent of the four components described above.

It should also be understood that HFO-1234yf or trans-HFO-1234ze or amixture thereof can be within a weight percent composition range formedby any two numbers in paragraphs (A1) and (A1′) supra. Similarly, HFC-32can be within a weight percent composition range formed by any twonumbers in paragraphs (B1) and (B1′) supra; HFC-152a can be within aweight percent composition range formed by any two numbers in paragraphs(C1) and (C1′) supra, and said at least one saturated HFC can be withina weight percent composition range formed by any two numbers inparagraph Dl.

Compositions of note include:

-   -   compositions comprising from about 56 to about 98 weight percent        HFO-1234yf or trans-HFO-1234ze or a mixture thereof; from about        1 to about 29 weight percent HFC-32; and from about 1 to about        18 weight percent HFC-152a, HFO-1243zf, or mixtures thereof;        compositions comprising from about 60 to about 90 weight percent        HFO-1234yf or trans-HFO-1234ze or a mixture thereof; from about        5 to about 25 weight percent HFC-32; and from about 5 to about        15 weight percent HFC-152a, HFO-1243zf, or mixtures thereof;        compositions comprising from about 75 to about 85 weight percent        HFO-1234yf or trans-HFO-1234ze or a mixture thereof; about 10        weight percent HFC-32; and from about 5 to about 15 weight        percent HFC-152a, HFO-1243zf, or mixtures thereof; and        compositions comprising from about 58 to about 73.5 weight        percent HFO-1234yf or trans-HFO-1234ze or a mixture thereof,        about 21.5 weight percent HFC-32, and from about 5 to about 20        weight percent HFC-152a, HFO-1243zf, or mixtures thereof.

Of significant utility, for this embodiment, are compositions comprisingfrom about 56 to about 98 weight percent HFO-1234yf or HFO-1234ze or amixture thereof; from about 1 to about 43 weight percent HFC-32; andfrom about 1 to about 18 weight percent HFC-152a, HFO-1243zf, ormixtures thereof;. Of note are compositions comprising about 75-85weight percent HFO-1234yf, about 10 weight percent HFC-32, and about5-15 weight percent HFC-152a, HFO-1243zf, or mixtures thereof. Thesecompositions provide low GWP replacements for R-134a.

Also of significant utility, for this embodiment, are compositionscomprising from about 56 to about 98 weight percent HFO-1234yf orHFO-1234ze or a mixture thereof; from about 1 to about 43 weight percentHFC-32; and from about 1 to about 15 weight percent HFC-152a,HFO-1243zf, or mixtures thereof.

Also of utility are compositions comprising from about 58 to about 74weight percent HFO-1234yf, about 21.5 weight percent HFC-32, and fromabout 5 to about 20 weight percent HFC-152a, which provide low GWPreplacements for R-22. Also, compositions comprising from about 58 toabout 74 weight percent HFO-1234yf, about 21.5 weight percent HFC-32,and from about 5 to about 20 weight percent HFC-152a, HFO-1243zf, ormixtures thereof, which provide low GWP replacements for R-407C.

Also of utility are compositions comprising from about 56 weight percentto about 72 weight percent HFO-1234yf; from about 8 weight percent toabout 39 weight percent HFC-32; and from about 5 weight percent to about20 weight percent HFC-152a, that provide low GWP replacements for R-22.Also compositions comprising from about 56 weight percent to about 72weight percent HFO-1234yf; from about 8 weight percent to about 39weight percent HFC-32; and from about 5 weight percent to about 20weight percent HFC-152a, that provide low GWP replacements for R-407C.

Also of particular utility are compositions comprising from about 56weight percent to about 62 weight percent HFO-1234yf; from about 8weight percent to about 29 weight percent HFC-32; from about 5 weightpercent to about 20 weight percent HFC-152a; and about 10 weight percentHFC-134a, that provide low GWP replacements for R-22. Also compositionscomprising from about 56 weight percent to about 62 weight percentHFO-1234yf; from about 8 weight percent to about 29 weight percentHFC-32; from about 5 weight percent to about 20 weight percent HFC-152a;and about 10 weight percent HFC-134a, that provide low GWP replacementsfor R-407C.

Of particular utility, for this embodiment, are compositions comprisingfrom about 56 to about 98 weight percent trans-HFO-1234ze; from about 1to about 43 weight percent HFC-32; and from about 1 to about 20 weightpercent HFC-152a, HFO-1243zf, or mixtures thereof.

Also of note are compositions comprising from about 75 to about 85weight percent trans-HFO-1234ze, about 10 weight percent HFC-32, andfrom about 5 to about 15 weight percent HFC-152a, HFO-1243zf, ormixtures thereof, which provide low GWP replacements for R-134a withimproved cooling performance.

In another embodiment, compositions comprising from about 37 to about 53weight percent trans-HFO-1234ze, about 42.5 weight percent HFC-32, andfrom about 5 to about 20 weight percent HFC-152a, HFO-1243zf, ormixtures thereof, provide low GWP replacements for R-404A.

Exemplary Embodiment 2

In a second exemplary embodiment of the present invention, thecomposition comprises three components: (A) HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; (B) HFC-32; and (C) HFC-152a;wherein said HFC-32 component is less than about 29 weight percent byweight of the total composition. But at the same time, some amount ofHFO-1234yf or trans-HFO-1234ze or a mixture thereof and some amount ofHFC-152a, HFO-1243zf, or mixture thereof are always present in thecompositions of the present invention.

For the compositions of this embodiment:

-   (A2) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content can    be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%,    14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%,    27%, 28%, 29% 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%,    41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%,    54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%,    67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%,    80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%,    93%, 94%, 95%, 96%, 97%, 98%, or about 99% by weight of the    composition;-   (B2) HFC-32 can be any number within the range of from about 1% to    about 29%, for example, HFC-32 can be about 1%, 2%, 3%, 4%, 5%, 6%,    7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%,    21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, or about 29%, by weight of    the composition; and-   (C2) HFC-152a content can be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%,    9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%,    23%, 24%, 25%, 26%, 27%, 28%, 29% 30%, 31%, 32%, 33%, 34%, 35%, 36%,    37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%,    50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%,    63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%,    76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%,    89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or about 99% by    weight of the composition.    For the compositions of this embodiment:-   (A2′) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content    can also be a weight percent number that is in between the specific    weight percent numbers cited supra. For example, HFO-1234yf or    trans-HFO-1234ze or a mixture thereof can be about 0.5%, 1.5%, 2.5%,    3.5%, 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%,    13.5%, 14.5%, 15.5%, 16.5, 17.5, 18.5, 19.5%, 20.5%, 21.5%, 22.5%,    23.5%, 24.5%, 25.5%, 26.5%, 27.5%, 28.5%, 29.5%, 30.5%, 31.5%,    32.5%, 33.5%, 34.5%, 35.5%, 36.5%, 37.5%, 38%, 39.5%, 40.5%, 41.5%,    42.5%, 43.5%, 44.5%, 45.5%, 46.5%, 47.5%, 48.5%, 49.5%, 50.5%,    51.5%, 52.5%, 53.5%, 54.5%, 55.5%, 56.5%, 57.5%, 58.5%, 59.5%,    60.5%, 61.5%, 62.5%, 63.5%, 64.5%, 65.5%, 66.5%, 67.5%, 68.5%,    69.5%, 70.5%, 71.5%, 72.5%, 73.5%, 74.5%, 75.5%, 76.5%, 77.5%,    78.5%, 79.5%, 80.5%, 81.5%, 82.5%, 83.5%, 84.5%, 85.5.%, 86.5%,    87.5% 88.5%, 89.5%, 90.5%, 91.5%, 92.5%, 93.5%, 94.5%, 95.5.%,    96.5%, 97.5%, or about 98.5%, by weight of the composition;-   (B2′) HFC-32 content can also be a weight percent number that is in    between the specific weight percent numbers cited supra. For    example, HFC-32 can be about 0.5%, 1.5%, 2.5%, 3.5%, 4.5%, 5.5%,    6.5%, 7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%, 13.5%, 14.5%, 15.5%,    16.5, 17.5, 18.5, 19.5%, 20.5%, 21.5%, 22.5%, 23.5%, 24.5%, 25.5%,    26.5%, 27.5%, or about 28.5% by weight of the composition;-   (C2′) HFC-152a content can also be a weight percent number that is    in between the specific weight percent numbers cited supra. For    example, HFC-152a can be about 1.5%, 2.5%, 3.5%, 4.5%, 5.5%, 6.5%,    7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%, 13.5%, 14.5%, 15.5%, 16.5,    17.5, 18.5, 19.5%, 20.5%, 21.5%, 22.5%, 23.5%, 24.5%, 25.5%, 26.5%,    27.5%, 28.5%, 29.5%, 30.5%, 31.5%, 32.5%, 33.5%, 34.5%, 35.5%,    36.5%, 37.5%, 38%, 39.5%, 40.5%, 41.5%, 42.5%, 43.5%, 44.5%, 45.5%,    46.5%, 47.5%, 48.5%, 49.5%, 50.5%, 51.5%, 52.5%, 53.5%, 54.5%,    55.5%, 56.5%, 57.5%, 58.5%, 59.5%, 60.5%, 61.5%, 62.5%, 63.5%,    64.5%, 65.5%, 66.5%, 67.5%, 68.5%, 69.5%, 70.5%, 71.5%, 72.5%,    73.5%, 74.5%, 75.5%, 76.5%, 77.5%, 78.5%, 79.5%, 80.5%, 81.5%,    82.5%, 83.5%, 84.5%, 85.5.%, 86.5%, 87.5% 88.5%, 89.5%, 90.5%,    91.5%, 92.5%, 93.5%, 94.5%, 95.5.%, 96.5%, 97.5%, or about 98.5%, by    weight of the composition.-   (D2) In an alternative embodiment, at least one saturated HFCs may    also be included in the compositions described above. The weight    percent of said at least one saturated HFC to the total weight of    the composition can be in the range of from about 0% to about 10%.    The weight percent of said at least one saturated HFC in the    composition can be about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%,    4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, and 10%.

Similarly, other numbers in between the integer numbers supra, forexample, 56.1, 56.2, 56.3 and the like can also be included for thecontent of the four components described above.

It should also be understood that HFO-1234yf or trans-HFO-1234ze or amixture thereof can be within a weight percent composition range formedby any two numbers in paragraphs (A2) and (A2′) supra. Similarly, HFC-32can be within a weight percent composition range formed by any twonumbers in paragraphs (B2) and (B2′) supra; HFC-152a can be within aweight percent composition range formed by any two numbers in paragraphs(C2) and (C2′) supra, and said at least one saturated HFC can be withina weight percent composition range formed by any two numbers inparagraph D2.

Of particular utility, for this embodiment, are compositions comprisingfrom about 56 to about 98 weight percent HFO-1234yf or HFO-1234ze or amixture thereof; from about 1 to about 29 weight percent HFC-32; andfrom about 1 to about 15 weight percent HFC-152a.

Also of particular utility are compositions comprising from about 75 toabout 85 weight percent HFO-1234yf or trans-HFO-1234ze or a mixturethereof; about 10 weight percent HFC-32; and from about 5 to about 15weight percent HFC-152a, HFO-1243zf, or mixtures thereof.

Also of particular utility are compositions comprising from about 58 toabout 73.5 weight percent HFO-1234yf or trans-HFO-1234ze or a mixturethereof, about 21.5 weight percent HFC-32, and from about 5 to about 20weight percent HFC-152a, HFO-1243zf, or mixtures thereof.

Of note are compositions comprising from about 75 to about 85 weightpercent HFO-1234yf, about 10 weight percent HFC-32, and from about 5 toabout 15 weight percent HFC-152a, HFO-1243zf, or mixtures thereof. Thesecompositions provide low GWP replacements for R-134a.

Exemplary Embodiment 3

In a third exemplary embodiment of the present invention, thecomposition comprises three components: (A) HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; (B) HFC-32; and (C) HFC-152a;wherein said HFC-152a is greater than about 56 weight percent. But atthe same time, some amount of HFO-1234yf or trans-HFO-1234ze or amixture thereof and some amount of HFC-32 are always present in thecompositions of the present invention.

For the compositions of this embodiment:

-   (A3) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content can    be any number within the range of from about 1% to about 43%, for    example, HFO-1234yf or trans-HFO-1234ze or a mixture thereof can be    about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%,    15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%,    28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%,    41%, 42%, or about 43% by weight of the composition;-   (B3) HFC-32 can be any number within the range of from about 1% to    about 43%, for example, HFC-32 can be about 1%, 2%, 3%, 4%, 5%, 6%,    7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%,    21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%,    34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, or about 43% by weight    of the composition; and-   (C3) HFC-152a content can be about 56%, 57%, 58%, 59%, 60%, 61%,    62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%,    75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%,    88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, or about 98% by    weight of the composition.    For the compositions of this embodiment:-   (A3′) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content    can also be a weight percent number that is in between the specific    weight percent numbers cited supra. For example, HFO-1234yf or    trans-HFO-1234ze or a mixture thereof can be about 0.5%, 1.5%, 2.5%,    3.5%, 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%,    13.5%, 14.5%, 15.5%, 16.5, 17.5, 18.5, 19.5%, 20.5%, 21.5%, 22.5%,    23.5%, 24.5%, 25.5%, 26.5%, 27.5%, 28.5%, 29.5%, 30.5%, 31.5%,    32.5%, 33.5%, 34.5%, 35.5%, 36.5%, 37.5%, 38%, 39.5%, 40.5%, 41.5%,    42.5%, or about 43.5% by weight of the composition;-   (B3′) HFC-32 content can also be a weight percent number that is in    between the specific weight percent numbers cited supra. For    example, HFC-32 can be about 0.5%, 1.5%, 2.5%, 3.5%, 4.5%, 5.5%,    6.5%, 7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%, 13.5%, 14.5%, 15.5%,    16.5, 17.5, 18.5, 19.5%, 20.5%, 21.5%, 22.5%, 23.5%, 24.5%, 25.5%,    26.5%, 27.5%, 28.5%, 29.5%, 30.5%, 31.5%, 32.5%, 33.5%, 34.5%,    35.5%, 36.5%, 37.5%, 38%, 39.5%, 40.5%, 41.5%, 42.5%, or about 43.5%    by weight of the composition; and-   (C3′) HFC-152a content can also be a weight percent number that is    in between the specific weight percent numbers cited supra. For    example, HFC-152a can be about 56.5%, 57.5%, 58.5%, 59.5%, 60.5%,    61.5%, 62.5%, 63.5%, 64.5%, 65.5%, 66.5%, 67.5%, 68.5%, 69.5%,    70.5%, 71.5%, 72.5%, 73.5%, 74.5%, 75.5%, 76.5%, 77.5%, 78.5%,    79.5%, 80.5%, 81.5%, 82.5%, 83.5%, 84.5%, 85.5%, 86.5%, 87.5%,    88.5%, 89.5%, 90.5%, 91.5%, 92.5%, 93.5%, 94.5%, 95.5%, 96.5%,    97.5%, or about 98.5% by weight of the composition.-   (D3) In an alternative embodiment, at least one saturated HFC may    also be included in the compositions described above. The weight    percent of said at least one saturated HFC to the total weight of    the composition can be in the range of from about 0% to about 10%.    The weight percent of said at least one saturated HFC in the    composition can be about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%,    4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, and 10%.

Similarly, other numbers in between the integer numbers supra, forexample, 56.1, 56.2, 56.3 and the like can also be included for thecontent of the four components described above.

It should also be understood that HFO-1234yf or trans-HFO-1234ze or amixture thereof can be within a weight percent composition range formedby any two numbers in paragraphs (A3) and (A3′) supra. Similarly, HFC-32can be within a weight percent composition range formed by any twonumbers in paragraphs (B3) and (B3′) supra; HFC-152a can be within aweight percent composition range formed by any two numbers in paragraphs(C3) and (C3′) supra, and said at least one saturated HFC can be withina weight percent composition range formed by any two numbers inparagraph D3.

Of particular utility are compositions comprising from about 1 weightpercent to about 43 weight percent HFO-1234yf or trans-HFO-1234ze or amixture thereof; from about 1 weight percent to about 43 weight percentHFC-32; and from about 56 weight percent to about 98 weight percent152a.

Also of particular utility are compositions comprising from about 20weight percent to about 30 weight percent HFO-1234yf or trans-HFO-1234zeor a mixture thereof; about 10 weight percent HFC-32; and from about 60weight percent to about 70 weight percent HFC-152a, which provide lowGWP replacements for R-134a.

Exemplary Embodiment 4

In a fourth exemplary embodiment of the present invention, thecomposition of the present invention comprises three components: (A)HFO-1234yf or trans-HFO-1234ze or a mixture thereof; (B) HFC-32; and (C)HFC-152a, HFO-1243zf, or mixture thereof; wherein said HFC-152a,HFO-1243zf or mixture thereof is in the range of from about 14 weightpercent to about 16 weight percent.

For the compositions of this embodiment:

-   (A4) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content can    be any number within the range of from about 0.5% to about 85.5%    including every number within the range that is 0.1% increment over    the previous number, by weight of the composition;-   (B4) HFC-32 can be any number within the range of from about 0.5% to    about 85.5% including every number within the range that is 0.1%    increment over the previous number, by weight of the composition;    and-   (C4) HFC-152a, HFO-1243zf or mixture thereof content can be about    14%, 14.5%, 15%, 15.5%, or about 16% by weight of the composition.-   (D4) In an alternative embodiment, at least one saturated HFC may    also be included in the compositions described above. The weight    percent of HFC-134a to the total weight of the composition can be in    the range of from about 0% to about 10%. The weight percent of    HFC-134a in the composition can be about 0.5%, 1%, 1.5%, 2%, 2.5%,    3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%,    9.5%, and 10%.

Similarly, other numbers in between the integer numbers supra, forexample, 56.1, 56.2, 56.3 and the like can also be included for thecontent of the four components described above.

It should also be understood that HFO-1234yf or trans-HFO-1234ze or amixture thereof can be within a weight percent composition range formedby any two numbers in paragraphs (A4) supra. Similarly, HFC-32 can bewithin a weight percent composition range formed by any two numbers inparagraphs (B4) supra; HFC-152a can be within a weight percentcomposition range formed by any two numbers in paragraphs (C4) supra,and said at least one saturated HFC can be within a weight percentcomposition range formed by any two numbers in paragraph D4.

Exemplary Embodiment 5

In a fifth exemplary embodiment of the present invention, thecomposition comprises three components: (A) HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; (B) HFC-32; and (C) HFC-152a,HFO-1243zf, or mixture thereof; wherein said HFC-32 component is greaterthan about 56% by weight of the total composition. But at the same time,some amount of HFO-1234yf or trans-HFO-1234ze or a mixture thereof andsome amount of HFC-152a, HFO-1243zf or mixture thereof are alwayspresent in the compositions of the present invention.

For the compositions of this embodiment:

-   (A5) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content can    be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%,    14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%,    27%, 28%, 29% 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%,    41%, 42%, or about 43% by weight of the composition;-   (B5) HFC-32 can be any number within the range of from about 1% to    about 29%, for example, HFC-32 can be about 56%, 57%, 58%, 59%, 60%,    61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%,    74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%,    87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or about    99% by weight of the composition; and-   (C5) HFC-152a content can be about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%,    9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%,    23%, 24%, 25%, 26%, 27%, 28%, 29% 30%, 31%, 32%, 33%, 34%, 35%, 36%,    37%, 38%, 39%, 40%, 41%, 42%, or about 43% by weight of the    composition.    For the compositions of this embodiment:-   (A5′) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content    can also be a weight percent number that is in between the specific    weight percent numbers cited supra. For example, HFO-1234yf or    trans-HFO-1234ze or a mixture thereof can be about 0.5%, 1.5%, 2.5%,    3.5%, 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%,    13.5%, 14.5%, 15.5%, 16.5, 17.5, 18.5, 19.5%, 20.5%, 21.5%, 22.5%,    23.5%, 24.5%, 25.5%, 26.5%, 27.5%, 28.5%, 29.5%, 30.5%, 31.5%,    32.5%, 33.5%, 34.5%, 35.5%, 36.5%, 37.5%, 38%, 39.5%, 40.5%, 41.5%,    42.5%, or about 43.5% by weight of the composition;-   (B5′) HFC-32 content can also be a weight percent number that is in    between the specific weight percent numbers cited supra. For    example, HFC-32 can be about 56.5%, 57.5%, 58.5%, 59.5%, 60.5%,    61.5%, 62.5%, 63.5%, 64.5%, 65.5%, 66.5%, 67.5%, 68.5%, 69.5%,    70.5%, 71.5%, 72.5%, 73.5%, 74.5%, 75.5%, 76.5%, 77.5%, 78.5%,    79.5%, 80.5%, 81.5%, 82.5%, 83.5%, 84.5%, 85.5.%, 86.5%, 87.5%    88.5%, 89.5%, 90.5%, 91.5%, 92.5%, 93.5%, 94.5%, 95.5.%, 96.5%,    97.5%, or about 98.5%, by weight of the composition;-   (C5′) HFC-152a content can also be a weight percent number that is    in between the specific weight percent numbers cited supra. For    example, HFC-152a can be about 0.5%, 1.5%, 2.5%, 3.5%, 4.5%, 5.5%,    6.5%, 7.5%, 8.5%, 9.5%, 10.5%, 11.5%, 12.5%, 13.5%, 14.5%, 15.5%,    16.5, 17.5, 18.5, 19.5%, 20.5%, 21.5%, 22.5%, 23.5%, 24.5%, 25.5%,    26.5%, 27.5%, 28.5%, 29.5%, 30.5%, 31.5%, 32.5%, 33.5%, 34.5%,    35.5%, 36.5%, 37.5%, 38%, 39.5%, 40.5%, 41.5%, 42.5%, 43.5%, 44.5%,    45.5%, 46.5%, 47.5%, 48.5%, 49.5%, 50.5%, 51.5%, 52.5%, 53.5%,    54.5%, 55.5%, 56.5%, 57.5%, 58.5%, 59.5%, 60.5%, 61.5%, 62.5%,    63.5%, 64.5%, 65.5%, 66.5%, 67.5%, 68.5%, 69.5%, 70.5%, 71.5%,    72.5%, 73.5%, 74.5%, 75.5%, 76.5%, 77.5%, 78.5%, 79.5%, 80.5%,    81.5%, 82.5%, 83.5%, 84.5%, 85.5.%, 86.5%, 87.5% 88.5%, 89.5%,    90.5%, 91.5%, 92.5%, 93.5%, 94.5%, 95.5.%, 96.5%, 97.5%, or about    98.5%, by weight of the composition.-   (D5) In an alternative embodiment, at least one saturated HFC may    also be included in the compositions described above. The weight    percent of said at least one saturated HFC to the total weight of    the composition can be in the range of from about 0% to about 10%.    The weight percent of at least one saturated HFC in the composition    can be about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%,    6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, and 10%.

Similarly, other numbers in between the integer numbers supra, forexample, 56.1, 56.2, 56.3 and the like can also be included for thecontent of the four components described above.

It should also be understood that HFO-1234yf or trans-HFO-1234ze or amixture thereof can be within a weight percent composition range formedby any two numbers in paragraphs (A5) and (A5′) supra. Similarly, HFC-32can be within a weight percent composition range formed by any twonumbers in paragraphs (B5) and (B5′) supra; HFC-152a can be within aweight percent composition range formed by any two numbers in paragraphs(C5) and (C5′) supra, and at least one saturated HFC can be within aweight percent composition range formed by any two numbers in paragraphD5.

In another embodiment, of particular utility are compositions comprisingfrom about 22 to about 38 weight percent HFO-1234yf, trans-HFO-1234ze,or a mixture thereof; about 57.5 weight percent HFC-32; and from about 5to about 20 weight percent HFC-152a, HFO-1243zf, or mixtures thereof,which provide low GWP replacements for R-404A.

Exemplary Embodiment 6

In a sixth exemplary embodiment of the present invention, thecomposition comprises three components: (A) HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; (B) HFC-32; and (C) HFC-152a,HFO-1243zf, or mixture thereof; wherein said composition comprisestrans-HFO-1234ze; HFC-32; and HFC-152a, HFO-1243zf or mixture thereof.

For the compositions of this embodiment:

-   (A6) trans-HFO-1234ze content can be from about 20 weight percent to    about 85 weight percent, for example, trans-HFO-1234ze can be about    20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% 30%, 31%, 32%, 33%,    34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%,    47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%,    60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%,    73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, or about    85% by weight of the composition;-   (B6) HFC-32 can be any number within the range of from about 10% to    about 58%, for example, HFC-32 can be about 10%, 11%, 12%, 13%, 14%,    15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%,    28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%,    41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%,    54%, 55%, 56%, 57%, or about 58% by weight of the composition; and-   (C6) HFC-152a content can be from about 5 weight percent to about 20    weight percent, for example, HFC-152a can be about 5%, 6%, 7%, 8%,    9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or about 20%    by weight of the composition.-   (D6) In an alternative embodiment, at least one saturated HFC may    also be included in the compositions described above. The weight    percent of said at least one saturated HFC to the total weight of    the composition can be in the range of from about 0% to about 10%.

The weight percent of at least one saturated HFC in the composition canbe about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%,6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, and 10%.

Similarly, other numbers in between the integer numbers supra, forexample, 20.1, 20.2, 20.3, 20.4, 20.5 and the like can also be includedfor the content of the three components described above.

It should also be understood that trans-HFO-1234ze can be within aweight percent composition range formed by any two numbers in paragraph(A6) supra. Similarly, HFC-32 can be within a weight percent compositionrange formed by any two numbers in paragraph (B6) supra; HFC-152a can bewithin a weight percent composition range formed by any two numbers inparagraphs (C6) supra, and at least one saturated HFC can be within aweight percent composition range formed by any two numbers in paragraphD6.

Of note are compositions comprising from about 20 weight percent toabout 85 weight percent trans-HFO-1234ze; from about 10 weight percentto about 58 weight percent (or 57.5 weight percent) HFC-32; and fromabout 5 weight percent to about 20 weight percent HFC-152a.

Of particular note are compositions comprising from about 20 weightpercent to about 30 weight percent trans-HFO-1234ze; about 10 weightpercent HFC-32; and from about 5 weight percent to about 20 weightpercent HFC-152a.

Also of particular note are compositions comprising from about 75 weightpercent to about 85 weight percent trans-HFO-1234ze; about 36 weightpercent HFC-32; and from about 5 weight percent to about 20 weightpercent HFC-152a. Also of particular note are compositions comprisingfrom about 44 weight percent to about 59 weight percenttrans-HFO-1234ze; about 42.5 weight percent HFC-32; and from about 5weight percent to about 20 weight percent HFC-152a.

Also of particular note are compositions comprising from about 37 weightpercent to about 23 weight percent trans-HFO-1234ze; about 42.5 weightpercent HFC-32; and from about 5 weight percent to about 20 weightpercent HFC-152a.

Also of particular note are compositions comprising from about 23 weightpercent to about 37 weight percent trans-HFO-1234ze; about 57.5 (orabout 58) weight percent HFC-32; and from about 5 weight percent toabout 20 weight percent HFC-152a.

Exemplary Embodiment 7

In a sixth exemplary embodiment of the present invention, thecomposition comprises three components: (A) HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; (B) HFC-32; and (C) HFC-152a,HFO-1243zf, or mixture thereof; wherein said HFO-1243zf or mixturethereof with HFC-152a is at most 20 weight percent of the total weightof said composition. But at the same time, some amount of HFO-1234yf ortrans-HFO-1234ze or a mixture thereof and some amount of HFC-32 arealways present in the compositions of the present invention.

For the compositions of this embodiment:

-   (A7) HFO-1234yf or trans-HFO-1234ze or a mixture thereof content can    be from about 56 weight percent to about 72 weight percent, for    example, trans-HFO-1234ze can be about 56%, 57%, 58%, 59%, 60%, 61%,    62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, or about 72% by    weight of the composition;-   (B7) HFC-32 can be any number within the range of from about 8% to    about 39%, for example, HFC-32 can be about 8%, 9%, 10%, 11%, 12%,    13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%,    26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, or    about 39% by weight of the composition; and-   (C7) HFC-152a, HFO-1243zf or mixture thereof content can be from    about 5 weight percent to about 20 weight percent, for example,    HFC-152a can be about 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%,    15%, 16%, 17%, 18%, 19%, or about 20% by weight of the composition.-   (D7) In an alternative embodiment, at least one saturated HFC may    also be included in the compositions described above. The weight    percent of said at least one saturated HFC to the total weight of    the composition can be in the range of from about 0% to about 10%.    The weight percent of at least one saturated HFC in the composition    can be about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%,    6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, and 10%.

Similarly, other numbers in between the integer numbers supra, forexample, 56.1, 56.2, 56.3, 56.4, 56.5 and the like can also be includedfor the content of the three components described above.

It should also be understood that HFO-1234yf, trans-HFO-1234ze ormixture thereof can be within a weight percent composition range formedby any two numbers in paragraph (A7) supra. Similarly, HFC-32 can bewithin a weight percent composition range formed by any two numbers inparagraph (B7) supra; HFC-152a can be within a weight percentcomposition range formed by any two numbers in paragraph (C7) supra, andat least one saturated HFC can be within a weight percent compositionrange formed by any two numbers in paragraph D7.

In another embodiment, a composition comprising from about 44 to 59weight percent HFO-1234yf; about 36 weight percent HFC-32; and fromabout 5 to 20 weight percent HFC-152a, HFO-1243zf, or mixtures thereof,which provide low GWP replacements for R-404A.

In another embodiment, compositions comprising from about 37 to about 53weight percent HFO-1234yf; about 42.5 weight percent HFC-32; and fromabout 5 to about 20 weight percent HFC-152a, HFO-1243zf, or mixturesthereof, which provide low GWP replacements for R-404A.

In another embodiment, compositions comprising from about 56 weightpercent to about 72 weight percent HFO-1234yf; from about 12 weightpercent to about 39 weight percent HFC-32; from 0 weight percent toabout 20 weight percent HFC-152a, HFO-1243zf, or mixtures thereof,provide low GWP replacements for R-22. Also, compositions comprisingfrom about 56 weight percent to about 72 weight percent HFO-1234yf; fromabout 12 weight percent to about 39 weight percent HFC-32; from 0 weightpercent to about 20 weight percent HFC-152a, HFO-1243zf, or mixturesthereof, provide low GWP replacements for R-407C.

In another embodiment, compositions comprising from about 56 weightpercent to about 62 weight percent HFO-1234yf; from about 8 weightpercent to about 29 weight percent HFC-32; from 0 weight percent toabout 10 weight percent HFC-152a; from 0 to about 20 weight percentHFO-1243zf; and about 10 weight percent HFC-134a, provide low GWPreplacements for R-22. Also, compositions comprising from about 56weight percent to about 62 weight percent HFO-1234yf; from about 8weight percent to about 29 weight percent HFC-32; from 0 weight percentto about 10 weight percent HFC-152a; from 0 to about 20 weight percentHFO-1243zf; and about 10 weight percent HFC-134a, provide low GWPreplacements for R-407C.

In another embodiment, compositions comprising from about 56 weightpercent to about 72 weight percent HFO-1234yf; from about 12 weightpercent to about 39 weight percent HFC-32; from 0 weight percent toabout 20 weight percent HFC-152a, HFO-1243zf, or mixtures thereof,provide low GWP replacements for R-22. Also, compositions comprisingfrom about 56 weight percent to about 72 weight percent HFO-1234yf; fromabout 12 weight percent to about 39 weight percent HFC-32; from 0 weightpercent to about 20 weight percent HFC-152a, HFO-1243zf, or mixturesthereof, provide low GWP replacements for R-407C.

In another embodiment, compositions comprising from about 56 weightpercent to about 62 weight percent HFO-1234yf; from about 8 weightpercent to about 29 weight percent HFC-32; from 0 weight percent toabout 10 weight percent HFC-152a; from 0 to about 20 weight percentHFO-1243zf; and about 10 weight percent HFC-134a, provide low GWPreplacements for R-22. Also, compositions comprising from about 56weight percent to about 62 weight percent HFO-1234yf; from about 8weight percent to about 29 weight percent HFC-32; from 0 weight percentto about 10 weight percent HFC-152a; from 0 to about 20 weight percentHFO-1243zf; and about 10 weight percent HFC-134a, provide low GWPreplacements for R-407C.

Other Preferred Embodiments

In a preferred embodiment, in the compositions described supra, said atleast one saturated HFC is HFC-134a.

In a further preferred embodiment, in the compositions described supracomprising either of the three components or the four components, thecooling capacity of the composition is at least 75% of the coolingcapacity of at least one refrigerant selected from the group consistingof existing refrigerants.

By “existing refrigerants” is meant at least one refrigerant selectedfrom

R-134a, R-22, R-407C, and R-404A. In a preferred embodiment, theexisting refrigerant to be replaced is R-134a, R-22, R-407C, R407A,R407F, R507, R422A, R422D, R417A, R437A, R438A, and R-404A. The coolingcapacity can be about 75%, 76%, 77%, 78%, 79%, 89%, 81%, 82%, 83%, 84%,85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%,99%, 100%, 101%, 102% 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%,11%, 112%, 113%, 114%, 115%, 116%, 1175, 118%, 119%, 120%, 121%, 122%,123%, 124%, 125%, 126, 127%, 128%, 129%, or about 130%.

For example, a composition comprising from about 75 to about 85 weightpercent HFO-1234yf or trans-HFO-1234ze or a mixture thereof, about 10weight percent HFC-32, and from about 5 to about 15 weight percentHFC-152a exhibits cooling capacity that is 125% of the cooling capacityof R-134a. In another example, composition comprising from about 58 toabout 73.5 weight percent HFO-1234yf or trans-HFO-1234ze or a mixturethereof, about 21.5 weight percent HFC-32, and from about 5 to about 20weight percent HFC-152a exhibits cooling capacity that is from 90-95% ofthe cooling capacity of R-22 and R-407C. Similarly, a compositioncomprising about 59 weight percent HFO-1234yf or trans-HFO-1234ze or amixture thereof, about 36 weight percent HFC-32 and about 5 weightpercent HFC-152a exhibits a cooling capacity that is about 103% of thecooling capacity of R-404A. In another example, composition comprisingfrom about 22 to about 38 weight percent HFO-1234yf or trans-HFO-1234zeor a mixture thereof, about 57.5 weight percent HFC-32 and from about 5to about 20 weight percent HFC-152a exhibits a cooling capacity that is114-121% of the cooling capacity of R-404A.

In another preferred embodiment, compositions of the present inventioncomprising either the three components or more than three components,have been found to provide reduced GWP as compared to existingrefrigerants such as R-134a, R-22, R-407C, and R-404A.

For example, a composition comprising from about 56 to about 62 weightpercent HFO-1234yf or trans-HFO-1234ze or a mixture thereof, from about23 to about 29 weight percent HFC-32, and from 14 to 16 weight percentHFC-152a has a GWP in the range of 150-300 as compared to a GWP of 1430for R-22, R-407C, and R-134a, and a GWP of 3922 for R-404A. In anotherexample, composition comprising from about 75 to about 85 weight percentHFO-1234yf or trans-HFO-1234ze or a mixture thereof, about 10 weightpercent HFC-32, and from about 5 to about 15 weight percent HFC-152aexhibits a GWP number in the range of 70-90. In yet another example, acomposition comprising from about 58 to about 73.5 weight percentHFO-1234yf or trans-HFO-1234ze or a mixture thereof, about 21.5 weightpercent HFC-32, and from about 5 to about 20 weight percent HFC-152aexhibits a GWP number of 150-175. Similarly, a composition comprisingabout 59 weight percent HFO-1234yf or trans-HFO-1234ze or a mixturethereof, about 36 weight percent HFC-32 and about 5 weight percentHFC-152a exhibits a GWP number of about 252. In another example,composition comprising from about 22 to about 38 weight percentHFO-1234yf or trans-HFO-1234ze or a mixture thereof, about 57.5 weightpercent HFC-32 and from about 5 to about 20 weight percent HFC-152aexhibits a GWP number in the range of 396-414.

In a preferred composition of the above embodiment, the HFC-152a is inthe range of from about 14 weight percent to about 16 weight percent.

Other preferred embodiments include (i) from 56 to about 69 weightpercent HFO-1234yf or trans-HFO-1234ze or a mixture thereof, 26-39weight percent HFC-32, and from about 4 to about 6 weight percentHFC-152a; (ii) from about 56 to about 62 weight percent HFO-1234yf ortrans-HFO-1234ze or a mixture thereof, from about 28 to about 34 weightpercent HFC-32, and (iii) from about 9 to about 11 weight percentHFC-152a; and (iv) from about 56 to about 62 weight percent HFO-1234yfor trans-HFO-1234ze or a mixture thereof, 23-29 weight percent HFC-32,and from 14 to 16 weight percent HFC-152a.

In a further preferred embodiment, in the compositions described supra,the ratio of HFO-1234yf or trans-HFO-1234ze or a mixture thereof toHFC-152a is in the range of from about 1 to about 20. The ratio can beabout 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2,2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6,3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0,5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4,6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8,7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2,9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3, 10.4, 10.5,10.6, 10.7, 10.8, 10.9, 11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7,11.8, 11.9, 12.0, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9,13.0, 13.1, 13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1,14.2, 14.3, 14.4, 14.5, 14.6, 14.7, 14.8, 14.9, 15.0, 15.1, 15.2, 15.3,15.4, 15.5, 15.6, 15.7, 15.8, 15.9, 16.0, 16.1, 16.2, 16.3, 16.4, 16.5,16.6, 16.7, 16.8, 16.9, 17.0, 17.1, 17.2, 17.3, 17.4, 17.5, 17.6, 17.7,17.8, 17.9, 18.0, 18.1, 18.2, 18.3, 18.4, 18.5, 18.6, 18.7, 18.9, 19.0,19.1, 19.2, 19.3, 19.4, 19.5, 19.6, 19.7, 19.8, 19.9, or 20.0.

In a preferred composition of the present invention, in compositionsdescribed above, it has been found, surprisingly, that in a narrow rangeof HFC-152a, of from about 14.5 weight percent to about 15.5 weightpercent, the compositions (three-component or more-than-three-component)have cooling capacity within ±25% of many of the existing refrigerants,particularly, R-22, R-404A, R-134a, and R-407C.

The present invention relates to azeotropic, near azeotropic andnon-azeotropic compositions.

Compositions with higher capacity than the refrigerant being replacedprovide reduced carbon fingerprint by allowing a lower charge size (lessrefrigerant will be necessary to achieve the same cooling effect).Therefore, even with a higher GWP such compositions may provide a netreduced environmental impact. Additionally, new equipment may bedesigned to provide even greater energy efficiency improvements, thusalso minimizing the environmental impact of using a new refrigerant.

In some embodiments, in addition to tetrafluoropropene, difluoromethane,and 1,1,-difluoroethane, the compositions may comprise optional othercomponents.

In some embodiments, the optional other components (also referred toherein as additives) in the compositions disclosed herein may compriseone or more components selected from the group consisting of lubricants,dyes (including UV dyes), solubilizing agents, compatibilizers,stabilizers, tracers, perfluoropolyethers, anti-wear agents, extremepressure agents, corrosion and oxidation inhibitors, metal surfaceenergy reducers, metal surface deactivators, free radical scavengers,foam control agents, viscosity index improvers, pour point depressants,detergents, viscosity adjusters, and mixtures thereof. Indeed, many ofthese optional other components fit into one or more of these categoriesand may have qualities that lend themselves to achieve one or moreperformance characteristic.

In some embodiments, one or more additive present in small amountsrelative to the overall composition. In some embodiments, the amount ofadditive(s) concentration in the disclosed compositions is from lessthan about 0.1 weight percent to as much as about 5 weight percent ofthe total composition. In some embodiments of the present invention, theadditives are present in the disclosed compositions in an amount betweenabout 0.1 weight percent to about 3.5 weight percent of the totalcomposition. The additive component(s) selected for the disclosedcomposition is selected on the basis of the utility and/or individualequipment components or the system requirements.

In some embodiments, the lubricant is a mineral oil lubricant. In someembodiments, the mineral oil lubricant is selected from the groupconsisting of paraffins (including straight carbon chain saturatedhydrocarbons, branched carbon chain saturated hydrocarbons, and mixturesthereof), naphthenes (including saturated cyclic and ring structures),aromatics (those with unsaturated hydrocarbons containing one or morering, wherein one or more ring is characterized by alternatingcarbon-carbon double bonds) and non-hydrocarbons (those moleculescontaining atoms such as sulfur, nitrogen, oxygen and mixtures thereof),and mixtures and combinations of thereof.

Some embodiments may contain one or more synthetic lubricant. In someembodiments, the synthetic lubricant is selected from the groupconsisting of alkyl substituted aromatics (such as benzene ornaphthalene substituted with linear, branched, or mixtures of linear andbranched alkyl groups, often generically referred to as alkylbenzenes),synthetic paraffins and napthenes, poly (alpha olefins), polyglycols(including polyalkylene glycols), dibasic acid esters, polyesters,neopentyl esters, polyvinyl ethers (PVEs), silicones, silicate esters,fluorinated compounds, phosphate esters, polycarbonates and mixturesthereof, meaning mixtures of the any of the lubricants disclosed in thisparagraph.

The lubricants as disclosed herein may be commercially availablelubricants. For instance, the lubricant may be paraffinic mineral oil,sold by BVA Oils as BVM 100 N, naphthenic mineral oils sold by CromptonCo. under the trademarks Suniso® 1GS, Suniso® 3GS and Suniso® 5GS,naphthenic mineral oil sold by Pennzoil under the trademark Sontex®372LT, naphthenic mineral oil sold by Calumet Lubricants under thetrademark Calumet® RO-30, linear alkylbenzenes sold by Shrieve Chemicalsunder the trademarks Zerol® 75, Zerol® 150 and Zerol® 500 and branchedalkylbenzene sold by Nippon Oil as HAB 22, polyol esters (POEs) soldunder the trademark Castrol® 100 by Castrol, United Kingdom,polyalkylene glycols (PAGs) such as RL-488A from Dow (Dow Chemical,Midland, Mich.), and mixtures thereof, meaning mixtures of any of thelubricants disclosed in this paragraph.

The lubricants used with the present invention may be designed for usewith hydrofluorocarbon refrigerants and may be miscible withcompositions as disclosed herein under compression refrigeration andair-conditioning apparatus' operating conditions. In some embodiments,the lubricants are selected by considering a given compressor'srequirements and the environment to which the lubricant will be exposed.

In the compositions of the present invention including a lubricant, thelubricant is present in an amount of less than 5.0 weight % to the totalcomposition. In other embodiments, the amount of lubricant is betweenabout 0.1 and 3.5 weight % of the total composition.

Notwithstanding the above weight ratios for compositions disclosedherein, it is understood that in some heat transfer systems, while thecomposition is being used, it may acquire additional lubricant from oneor more equipment components of such heat transfer system. For example,in some refrigeration, air conditioning and heat pump systems,lubricants may be charged in the compressor and/or the compressorlubricant sump. Such lubricant would be in addition to any lubricantadditive present in the refrigerant in such a system. In use, therefrigerant composition when in the compressor may pick up an amount ofthe equipment lubricant to change the refrigerant-lubricant compositionfrom the starting ratio.

In such heat transfer systems, even when the majority of the lubricantresides within the compressor portion of the system, the entire systemmay contain a total composition with as much as about 75 weight percentto as little as about 1.0 weight percent of the composition beinglubricant. In some systems, for example supermarket refrigerated displaycases, the system may contain about 3 weight percent lubricant (over andabove any lubricant present in the refrigerant composition prior tocharging the system) and 97 weight percent refrigerant. In anotherembodiment, in some systems, for example mobile air conditioningsystems, the system may contain about 20 weight percent lubricant (overand above any lubricant present in the refrigerant composition prior tocharging the system) and about 80 weight percent refrigerant.

The additive used with the compositions of the present invention mayinclude at least one dye. The dye may be at least one ultra-violet (UV)dye. The UV dye may be a fluorescent dye. The fluorescent dye may beselected from the group consisting of naphthalim ides, perylenes,coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes,naphthoxanthenes, fluoresceins, and derivatives of said dye, andcombinations thereof, meaning mixtures of any of the foregoing dyes ortheir derivatives disclosed in this paragraph.

In some embodiments, the disclosed compositions contain from about 0.001weight percent to about 1.0 weight percent UV dye. In other embodiments,the UV dye is present in an amount of from about 0.005 weight percent toabout 0.5 weight percent; and in other embodiments, the UV dye ispresent in an amount of from 0.01 weight percent to about 0.25 weightpercent of the total composition.

UV dye is a useful component for detecting leaks of the composition bypermitting one to observe the fluorescence of the dye at or in thevicinity of a leak point in an apparatus (e.g., refrigeration unit,air-conditioner or heat pump). The UV emission, e.g., fluorescence fromthe dye may be observed under an ultra-violet light. Therefore, if acomposition containing such a UV dye is leaking from a given point in anapparatus, the fluorescence can be detected at the leak point, or in thevicinity of the leak point.

The additive which may be used with the compositions of the presentinvention may include at least one solubilizing agent selected toimprove the solubility of one or more dye in the disclosed compositions.In some embodiments, the weight ratio of dye to solubilizing agentranges from about 99:1 to about 1:1. The solubilizing agents include atleast one compound selected from the group consisting of hydrocarbons,hydrocarbon ethers, polyoxyalkylene glycol ethers (such as dipropyleneglycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (suchas methylene chloride, trichloroethylene, chloroform, or mixturesthereof), esters, lactones, aromatic ethers, fluoroethers and1,1,1-trifluoroalkanes and mixtures thereof, meaning mixtures of any ofthe solubilizing agents disclosed in this paragraph.

In some embodiments, at least one compatibilizer is selected to improvethe compatibility of one or more lubricant with the disclosedcompositions. The compatibilizer may be selected from the groupconsisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycolethers (such as dipropylene glycol dimethyl ether), amides, nitriles,ketones, chlorocarbons (such as methylene chloride, trichloroethylene,chloroform, or mixtures thereof), esters, lactones, aromatic ethers,fluoroethers, 1,1,1-trifluoroalkanes, and mixtures thereof, meaningmixtures of any of the compatibilizers disclosed in this paragraph.

The solubilizing agent and/or compatibilizer may be selected from thegroup consisting of hydrocarbon ethers consisting of the etherscontaining only carbon, hydrogen and oxygen, such as dimethyl ether(DME) and mixtures thereof, meaning mixtures of any of the hydrocarbonethers disclosed in this paragraph.

The compatibilizer may be linear or cyclic aliphatic or aromatichydrocarbon compatibilizer containing from 3 to 15 carbon atoms. Thecompatibilizer may be at least one hydrocarbon, which may be selectedfrom the group consisting of at least propane, n-butane, isobutane,pentanes, hexanes, octanes, nonane, and decanes, among others.Commercially available hydrocarbon compatibilizers include but are notlimited to those from Exxon Chemical (USA) sold under the trademarksIsopar® H, a mixture of undecane (C₁₁) and dodecane (C₁₂) (a high purityC₁₁ to C₁₂ iso-paraffinic), Aromatic 150 (a C₉ to C₁₁ aromatic) (,Aromatic 200 (a C₉ to C₁₅ aromatic) and Naptha 140 (a mixture of C₅ toC₁₁ paraffins, naphthenes and aromatic hydrocarbons) and mixturesthereof, meaning mixtures of any of the hydrocarbons disclosed in thisparagraph.

The additive may alternatively be at least one polymeric compatibilizer.The polymeric compatibilizer may be a random copolymer of fluorinatedand non-fluorinated acrylates, wherein the polymer comprises repeatingunits of at least one monomer represented by the formulaeCH₂═C(R¹)CO₂R², CH₂═C(R³)C₆H₄R⁴, and CH₂═C(R⁵)C₆H₄XR⁶, wherein X isoxygen or sulfur; R¹, R³, and R⁵ are independently selected from thegroup consisting of H and C₁-C₄ alkyl radicals; and R², R⁴, and R⁶ areindependently selected from the group consisting of carbon-chain-basedradicals containing C, and F, and may further contain H, Cl, etheroxygen, or sulfur in the form of thioether, sulfoxide, or sulfone groupsand mixtures thereof. Examples of such polymeric compatibilizers includethose commercially available from E. I. du Pont de Nemours and Company(Wilmington, Del., 19898, USA) under the trademark Zonyl® PHS. Zonyl®PHS is a random copolymer made by polymerizing 40 weight percentCH₂═C(CH₃)CO₂CH₂CH₂(CF₂CF₂)_(m)F (also referred to as Zonyl®fluoromethacrylate or ZFM) wherein m is from 1 to 12, primarily 2 to 8,and 60 weight percent lauryl methacrylate (CH₂═C(CH₃)CO₂(CH₂)₁₁CH₃, alsoreferred to as LMA).

In some embodiments, the compatibilizer component contains from about0.01 to 30 weight percent (based on total amount of compatibilizer) ofan additive which reduces the surface energy of metallic copper,aluminum, steel, or other metals and metal alloys thereof found in heatexchangers in a way that reduces the adhesion of lubricants to themetal. Examples of metal surface energy reducing additives include thosecommercially available from DuPont under the trademarks Zonyl® FSA,Zonyl® FSP, and Zonyl® FSJ.

The additive which may be used with the compositions of the presentinvention may be a metal surface deactivator. The metal surfacedeactivator is selected from the group consisting of areoxalyl bis(benzylidene) hydrazide (CAS reg no. 6629-10-3),N,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS reg no.32687-78-8) ,2,2,′-oxamidobis-ethyl-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate (CASreg no. 70331-94-1), N,N′-(disalicyclidene)-1,2-diaminopropane (CAS regno. 94-91-7) and ethylenediaminetetra-acetic acid (CAS reg no. 60-00-4)and its salts, and mixtures thereof, meaning mixtures of any of themetal surface deactivators disclosed in this paragraph.

The additive used with the compositions of the present invention mayalternatively be a stabilizer selected from the group consisting ofhindered phenols, thiophosphates, butylated triphenylphosphorothionates,organo phosphates, or phosphites, aryl alkyl ethers, terpenes,terpenoids, epoxides, fluorinated epoxides, oxetanes, ascorbic acid,thiols, lactones, thioethers, amines, nitromethane, alkylsilanes,benzophenone derivatives, aryl sulfides, divinyl terephthalic acid,diphenyl terephthalic acid, ionic liquids, and mixtures thereof, meaningmixtures of any of the stabilizers disclosed in this paragraph.

The stabilizer may be selected from the group consisting of tocopherol;hydroquinone; t-butyl hydroquinone; monothiophosphates; anddithiophosphates, commercially available from Ciba Specialty Chemicals,Basel, Switzerland, hereinafter “Ciba”, under the trademark Irgalube®63; dialkylthiophosphate esters, commercially available from Ciba underthe trademarks Irgalube® 353 and Irgalube® 350, respectively; butylatedtriphenylphosphorothionates, commercially available from Ciba under thetrademark Irgalube® 232; amine phosphates, commercially available fromCiba under the trademark Irgalube® 349 (Ciba); hindered phosphites,commercially available from Ciba as Irgafos® 168 andTris-(di-tert-butylphenyl)phosphite, commercially available from Cibaunder the trademark Irgafos® OPH; (Di-n-octyl phosphite); and iso-decyldiphenyl phosphite, commercially available from Ciba under the trademarkIrgafos® DDPP; trialkyl phosphates, such as trimethyl phosphate,triethylphosphate, tributyl phosphate, trioctyl phosphate, andtri(2-ethylhexyl)phosphate; triaryl phosphates including triphenylphosphate, tricresyl phosphate, and trixylenyl phosphate; and mixedalkyl-aryl phosphates including isopropylphenyl phosphate (IPPP), andbis(t-butylphenyl)phenyl phosphate (TBPP); butylated triphenylphosphates, such as those commercially available under the trademarkSyn-O-Ad® including Syn-O-Ad® 8784; tert-butylated triphenyl phosphatessuch as those commercially available under the trademark Durad®620;isopropylated triphenyl phosphates such as those commercially availableunder the trademarks Durad® 220 and Durad®110; anisole;1,4-dimethoxybenzene; 1,4-diethoxybenzene; 1,3,5-trimethoxybenzene;myrcene, alloocimene, limonene (in particular, d-limonene); retinal;pinene; menthol; geraniol; farnesol; phytol; Vitamin A; terpinene;delta-3-carene; terpinolene; phellandrene; fenchene; dipentene;caratenoids, such as lycopene, beta carotene, and xanthophylls, such aszeaxanthin; retinoids, such as hepaxanthin and isotretinoin; bornane;1,2-propylene oxide; 1,2-butylene oxide; n-butyl glycidyl ether;trifluoromethyloxirane; 1,1-bis(trifluoromethyl)oxirane;3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd);3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-211 (Toagosei Co.,Ltd); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)-oxetane, such as OXT-212(Toagosei Co., Ltd); ascorbic acid; methanethiol (methyl mercaptan);ethanethiol (ethyl mercaptan); Coenzyme A; dimercaptosuccinic acid(DMSA); grapefruit mercaptan((R)-2-(4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine((R)-2-amino-3-sulfanyl-propanoic acid); lipoamide(1,2-dithiolane-3-pentanamide); 5,7-bis(1,1-dimethylethyl)-3-[2,3(or3,4)-dimethylphenyl]-2(3H)-benzofuranone, commercially available fromCiba under the trademark Irganox® HP-136; benzyl phenyl sulfide;diphenyl sulfide; diisopropylamine; dioctadecyl 3,3′-thiodipropionate,commercially available from Ciba under the trademark Irganox® PS 802(Ciba); didodecyl 3,3′-thiopropionate, commercially available from Cibaunder the trademark Irganox® PS 800;di-(2,2,6,6-tetramethyl-4-piperidyl)sebacate, commercially availablefrom Ciba under the trademark Tinuvin® 770;poly-(N-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate,commercially available from Ciba under the trademark Tinuvin® 622LD(Ciba); methyl bis tallow amine; bis tallow amine;phenol-alpha-naphthylamine; bis(dimethylamino)methylsilane (DMAMS);tris(trimethylsilyl)silane (TTMSS); vinyltriethoxysilane;vinyltrimethoxysilane; 2,5-difluorobenzophenone;2′,5′-dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone;benzyl phenyl sulfide; diphenyl sulfide; dibenzyl sulfide; ionicliquids; and mixtures and combinations thereof.

The additive used with the compositions of the present invention mayalternatively be an ionic liquid stabilizer. The ionic liquid stabilizermay be selected from the group consisting of organic salts that areliquid at room temperature (approximately 25° C.), those saltscontaining cations selected from the group consisting of pyridinium,pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium,thiazolium, oxazolium and triazolium and mixtures thereof ; and anionsselected from the group consisting of [BF₄]—, [PF₆]—, [SbF₆]—,[CF₃SO₃]—, [HCF₂CF₂SO₃]—, [CF₃HFCCF₂SO₃]—, [HCClFCF₂S₃]—, [(CF₃SO₂)₂N]—,[(CF₃CF₂SO₂)₂N]—, [(CF₃SO₂)₃C]—, [CF₃CO_(2]) 13 , and F— and mixturesthereof. In some embodiments, ionic liquid stabilizers are selected fromthe group consisting of emim BF₄ (1-ethyl-3-methylimidazoliumtetrafluoroborate); bmim BF₄ (1-butyl-3-methylimidazolium tetraborate);emim PF₆ (1-ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF₆(1-butyl-3-methylimidazolium hexafluorophosphate), all of which areavailable from Fluka (Sigma-Aldrich).

In some embodiments, the stabilizer may be a hindered phenol, which isany substituted phenol compound, including phenols comprising one ormore substituted or cyclic, straight chain, or branched aliphaticsubstituent group, such as, alkylated monophenols including2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butyl-4-ethylphenol;2,4-dimethyl-6-tertbutylphenol; tocopherol; and the like, hydroquinoneand alkylated hydroquinones including t-butyl hydroquinone, otherderivatives of hydroquinone; and the like, hydroxylated thiodiphenylethers, including 4,4′-thio-bis(2-methyl-6-tert-butylphenol);4,4′-thiobis(3-methyl-6-tertbutylphenol);2,2′-thiobis(4methyl-6-tert-butylphenol); and the like,alkylidene-bisphenols including:4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-bis(2,6-di-tert-butylphenol); derivatives of 2,2′- or4,4-biphenoldiols; 2,2′-methylenebis(4-ethyl-6-tertbutylphenol);2,2′-methylenebis(4-methyl-6-tertbutylphenol);4,4-butylidenebis(3-methyl-6-tert-butylphenol);4,4-isopropylidenebis(2,6-di-tert-butylphenol);2,2′-methylenebis(4-methyl-6-nonylphenol);2,2′-isobutylidenebis(4,6-dimethylphenol;2,2′-methylenebis(4-methyl-6-cyclohexylphenol, 2,2- or 4,4-biphenyldiolsincluding 2,2′-methylenebis(4-ethyl-6-tert-butylphenol);

butylated hydroxytoluene (BHT, or 2,6-di-tert-butyl-4-methylphenol),bisphenols comprising heteroatoms including2,6-di-tert-alpha-dimethylamino-p-cresol,4,4-thiobis(6-tert-butyl-m-cresol); and the like; acylaminophenols;2,6-di-tert-butyl-4(N,N′-dimethylaminomethylphenol); sulfides including;bis(3-methyl-4-hydroxy-5-tert-butylbenzyl)sulfide;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide and mixtures thereof,meaning mixtures of any of the phenols disclosed in this paragraph.

The additive which is used with compositions of the present inventionmay alternatively be a tracer. The tracer may be two or more tracercompounds from the same class of compounds or from different classes ofcompounds. In some embodiments, the tracer is present in thecompositions at a total concentration of about 50 parts per million byweight (ppm) to about 1000 ppm, based on the weight of the totalcomposition. In other embodiments, the tracer is present at a totalconcentration of about 50 ppm to about 500 ppm. Alternatively, thetracer is present at a total concentration of about 100 ppm to about 300ppm.

The tracer may be selected from the group consisting ofhydrofluorocarbons (HFCs), deuterated hydrofluorocarbons,perfluorocarbons, fluoroethers, brominated compounds, iodated compounds,alcohols, aldehydes and ketones, nitrous oxide and combinations thereof.Alternatively, the tracer may be selected from the group consisting offluoroethane, 1,1,1-trifluoroethane, 1,1,1,3,3,3-hexafluoropropane,1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,3,3-pentafluoropropane,1,1,1,3,3-pentafluorobutane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane,1,1,1,2,2,3,4,5,5,6,6,7,7,7-tridecafluoroheptane, iodotrifluoromethane,deuterated hydrocarbons, deuterated hydrofluorocarbons,perfluorocarbons, fluoroethers, brominated compounds, iodated compounds,alcohols, aldehydes, ketones, nitrous oxide (N₂O) and mixtures thereof.In some embodiments, the tracer is a blend containing two or morehydrofluorocarbons, or one hydrofluorocarbon in combination with one ormore perfluorocarbons.

The tracer may be added to the compositions of the present invention inpredetermined quantities to allow detection of any dilution,contamination or other alteration of the composition.

The additive which may be used with the compositions of the presentinvention may alternatively be a perfluoropolyether. A commoncharacteristic of perfluoropolyethers is the presence of perfluoroalkylether moieties. Perfluoropolyether is synonymous toperfluoropolyalkylether.

Other synonymous terms frequently used include “PFPE”, “PFAE”, “PFPEoil”, “PFPE fluid”, and “PFPAE”. In some embodiments, theperfluoropolyether has the formula ofCF₃—(CF₂)₂—O—[CF(CF₃)—CF₂—O]j′-R′f, and is commercially available fromDuPont under the trademark Krytox®. In the immediately precedingformula, j′ is 2-100, inclusive and R′f is CF₂CF₃, a C3 to C6perfluoroalkyl group, or combinations thereof.

Other PFPEs, commercially available from Ausimont of Milan, Italy, andMontedison S.p.A., of Milan, Italy, under the trademarks Fomblin® andGalden®, respectively, and produced by perfluoroolefin photooxidation,can also be used.

PFPE commercially available under the trademark Fomblin®-Y can have theformula of CF₃O(CF₂CF(CF₃)—O—)_(m)′(CF₂—O—)_(n)′—R_(1f). Also suitableis CF₃O[CF₂CF(CF₃)O]_(m)′(CF₂CF₂O)_(o)′(CF₂O)_(n)—R_(1f). In theformulae R_(1f) is CF₃, C₂F₅, C₃F₇, or combinations of two or morethereof ; (m′+n′) is 8-45, inclusive; and m/n is 20-1000, inclusive; o′is 1; (m′+n′+o′) is 8-45, inclusive; m′/n′ is 20-1000, inclusive.

PFPE commercially available under the trademark Fomblin® -Z can have theformula of CF₃O(CF₂CF₂—O—)_(p)′(CF₂—O)_(q)′CF₃ where (p′+q′) is 40-180and p′/q′ is 0.5-2, inclusive.

Another family of PFPE, commercially available under the trademarkDemnum™ from Daikin Industries, Japan, can also be used. It can beproduced by sequential oligomerization and fluorination of2,2,3,3-tetrafluorooxetane, yielding the formula ofF-[(CF₂)₃—O]_(t)′—R_(2f) where R_(2f) is CF₃, C₂F₅, or combinationsthereof and t′ is 2-200, inclusive.

In some embodiments, the PFPE is unfunctionalized. In anunfunctionalized perfluoropolyether, the end group can be branched orstraight chain perfluoroalkyl radical end groups. Examples of suchperfluoropolyethers can have the formula ofC_(r)′F_((24′+1))-A-C_(r)′F_((2r′+1)) in which each r′ is independently3 to 6; A can be O—(CF(CF₃)CF₂—O)_(w)′, O—(CF₂—O)_(x)′(CF₂CF₂—O)_(y)′,O—(C₂F₄—O)_(w)′, O—(C₂F₄—O)_(x)′(C₃F₆—O)_(y)′,O—(CF(CF₃)CF₂—O)_(x)′(CF₂—O)_(y)′, O—(CF₂CF₂CF₂—O)_(w)′,O—(CF(CF₃)CF₂—O)_(x)′(CF₂CF₂—O)_(y)′—(CF₂—O)_(z)′, or combinations oftwo or more thereof; preferably A is O—(CF(CF₃)CF₂—O)_(w)′,O—(C₂F₄—O)_(w)′, O—(C₂F₄—O)_(x)′(C₃F₆—O)_(y)′, O—(CF₂CF₂CF₂—O)_(w)′, orcombinations of two or more thereof; w′ is 4 to 100; x′ and y′ are eachindependently 1 to 100. Specific examples include, but are not limitedto, F(CF(CF₃)—CF₂—O)₉—CF₂CF₃, F(CF(CF₃)—CF₂—O)₉—CF(CF₃)₂, andcombinations thereof. In such PFPEs, up to 30% of the halogen atoms canbe halogens other than fluorine, such as, for example, chlorine atoms.

In other embodiments, the two end groups of the perfluoropolyether,independently, may be functionalized by the same or different groups. Afunctionalized PFPE is a PFPE wherein at least one of the two end groupsof the perfluoropolyether has at least one of its halogen atomssubstituted by a group selected from esters, hydroxyls, amines, amides,cyanos, carboxylic acids, sulfonic acids or combinations thereof.

In some embodiments, representative ester end groups include —COOCH₃,—COOCH₂CH₃, —CF₂COOCH₃, —CF₂COOCH₂CH₃, —CF₂CF₂COOCH₃, —CF₂CF₂COOCH₂CH₃,—CF₂CH₂COOCH₃, —CF₂CF₂CH₂COO CH₃, —CF₂CH₂CH₂COOCH₃, —CF₂CF₂CH₂CH₂COOCH₃.

In some embodiments, representative hydroxyl end groups include —CF₂OH,—CF₂CF₂OH, —CF₂CH₂OH, —CF₂CF₂CH₂OH, —CF₂CH₂CH₂OH, —CF₂CF₂CH₂CH₂OH.

In some embodiments, representative amine end groups include —CF₂NR¹R²,—CF₂CF₂NR¹R², —CF₂CH₂NR¹R², —CF₂CF₂CH₂NR¹R², —CF₂CH₂CH₂NR¹R²,—CF₂CF₂CH₂CH₂NR¹R², wherein R¹ and R² are independently H, CH₃, orCH₂CH₃.

In some embodiments, representative amide end groups include—CF₂C(O)NR¹R², —CF₂CF₂C(O)NR¹R², —CF₂CH₂C(O)NR¹R², —CF₂C F₂CH₂C(O)NR¹R²,—CF₂CH₂CH₂C(O)NR¹R², —CF₂CF₂CH₂CH₂C(O)NR¹R², wherein R¹ and R² areindependently H, CH₃, or CH₂CH₃.

In some embodiments, representative cyano end groups include —CF₂CN,—CF₂CF₂CN, —CF₂CH₂CN, —CF₂CF₂CH₂CN, —CF₂CH₂CH₂C N, —CF₂CF₂CH₂CH₂CN.

In some embodiments, representative carboxylic acid end groups include—CF₂COOH, —CF₂CF₂COOH, —CF₂CH₂COOH, —-CF₂CF₂CH₂COOH, —CF₂CH₂CH₂COOH,—CF₂CF₂CH₂CH₂COOH.

In some embodiments, the sulfonic acid end groups is selected from thegroup consisting

of —S(O)(O)OR³, —S(O)(O)R⁴, —CF₂OS(O)(O)OR³, —CF₂CF₂OS(O)(O)OR³,—CF₂CH₂OS(O)(O)OR³, —CF₂CF₂CH₂OS(O)(O)OR³, —CF₂CH₂CH₂OS(O)(O) OR³,—CF₂CF₂CH₂CH₂OS(O)(O)OR³, —CF₂S(O)(O)OR³, —CF₂CF₂S(O)(O)O R³,—CF₂CH₂S(O)(O)OR³, —CF₂CF₂CH₂S(O)(O)OR³, —CF₂CH₂CH₂S(O)(O)O R³,—CF₂CF₂CH₂CH₂S(O)(O)OR³, —CF₂OS(O)(O)R⁴, —CF₂CF₂OS(O)(O)R⁴,—CF₂CH₂OS(O)(O)R⁴, —CF₂CF₂CH₂OS(O)(O)R⁴, —CF₂CH₂CH₂OS(O)(O)R⁴,—CF₂CF₂CH₂CH₂OS(O)(O)R⁴, wherein R³ is H, CH₃, CH₂CH₃, CH₂CF₃, CF₃, orCF₂CF₃, R⁴ is CH₃, CH₂CH₃, CH₂CF₃, CF₃, or CF₂CF₃.

The additives may be members of the triaryl phosphate family of EP(extreme pressure) lubricity additives, such as butylated triphenylphosphates (BTPP), or other alkylated triaryl phosphate esters, such asthose sold under the trademark Syn-0-Ad® 8478 from Akzo Chemicals,tricresyl phosphates and related compounds. Additionally, the metaldialkyl dithiophosphates (e.g., zinc dialkyl dithiophosphate (or ZDDP),including the commercially available Lubrizol 1375 and other members ofthis family of chemicals is used in compositions of the disclosedcompositions. Other antiwear additives include natural product oils andasymmetrical polyhydroxyl lubrication additives, such as thecommercially available Synergol TMS (International Lubricants).

In some embodiments, stabilizers such as antioxidants, free radicalscavengers, and water scavengers and mixtures thereof are included. Suchadditives in this category can include, but are not limited to,butylated hydroxy toluene (BHT), epoxides, and mixtures thereof.

Corrosion inhibitors include dodecyl succinic acid (DDSA), aminephosphate (AP), oleoyl sarcosine, imidazone derivatives and substitutedsulfonates.

In one embodiment, the compositions disclosed herein may be prepared byany convenient method to combine the desired amounts of the individualcomponents. A preferred method is to weigh the desired component amountsand thereafter combine the components in an appropriate vessel.Agitation may be used, if desired.

In another embodiment, the compositions disclosed herein may be preparedby a method comprising (i) reclaiming a volume of one or more componentsof the refrigerant compositions disclosed herein from at least onerefrigerant container, (ii) removing impurities sufficiently to enablereuse of said one or more of the reclaimed components, (iii) andoptionally, combining all or part of said reclaimed volume of componentswith at least one additional refrigerant composition or component inorder to produce a composition described in the various embodimentsherein.

A refrigerant container may be any container in which is stored arefrigerant blend composition that has been used in a refrigerationapparatus, air-conditioning apparatus or heat pump apparatus. Saidrefrigerant container may be the refrigeration apparatus,air-conditioning apparatus or heat pump apparatus in which therefrigerant blend was used. Additionally, the refrigerant container maybe a storage container for collecting reclaimed refrigerant blendcomponents, including but not limited to pressurized gas cylinders.

Residual refrigerant means any amount of refrigerant blend orrefrigerant blend component that may be moved out of the refrigerantcontainer by any method known for transferring refrigerant blends orrefrigerant blend components.

Impurities may be any component that is in the refrigerant blend orrefrigerant blend component due to its use in a refrigeration apparatus,air-conditioning apparatus or heat pump apparatus. Such impuritiesinclude but are not limited to refrigeration lubricants, being thosedescribed earlier herein, particulates including but not limited tometal, metal salt or elastomer particles, that may have come out of therefrigeration apparatus, air-conditioning apparatus or heat pumpapparatus, and any other contaminants that may adversely affect theperformance of the refrigerant blend composition.

Such impurities may be removed sufficiently to allow reuse of therefrigerant blend or refrigerant blend component without adverselyaffecting the performance or equipment within which the refrigerantblend or refrigerant blend component will be used.

It may be necessary to provide additional refrigerant blend orrefrigerant blend component to the residual refrigerant blend orrefrigerant blend component in order to produce a composition that meetsthe specifications required for a given product. For instance, if arefrigerant blend has 3 components in a particular weight percentagerange, it may be necessary to add one or more of the components in agiven amount in order to restore the composition to within thespecification limits.

Compositions of the present invention have zero ozone depletionpotential and low global warming potential (GWP). Additionally, thecompositions of the present invention will have global warmingpotentials that are less than many hydrofluorocarbon refrigerantscurrently in use.

One aspect of the present invention is to provide a refrigerant with aglobal warming potential of less than 1000, less than 700, less than500, less than 400, less than 300, or less than 150, less than 100.

Methods of use

The compositions disclosed herein are useful as heat transfercompositions, aerosol propellants, foaming agents, blowing agents,solvents, cleaning agents, carrier fluids, displacement drying agents,buffing abrasion agents, polymerization media, expansion agents forpolyolefins and polyurethane, gaseous dielectrics and power cycleworking fluids. Additionally, in liquid or gaseous form, the disclosedcompositions may act as working fluids used to carry heat from a heatsource to a heat sink. Such heat transfer compositions may also beuseful as refrigerants in a cycle wherein the fluid undergoes phasechanges; that is, from a liquid to a gas and back or vice versa.

In many applications, some embodiments of the disclosed compositions areuseful as refrigerants and provide at least comparable coolingperformance (meaning cooling capacity and energy efficiency) as therefrigerant for which a replacement is being sought.

In some embodiments, the compositions disclosed herein are useful forany positive displacement compressor system designed for any number ofheat transfer compositions. Additionally, many of the compositionsdisclosed are useful in new equipment utilizing positive displacementcompressors to provide similar performance to the aforementionedrefrigerants.

In one embodiment, disclosed herein is a process to produce coolingcomprising condensing a composition as disclosed herein and thereafterevaporating said composition in the vicinity of a body to be cooled.

In another embodiment, disclosed herein is a process to produce heatcomprising condensing a composition as disclosed herein in the vicinityof a body to be heated and thereafter evaporating said composition.

In some embodiments, the use of the above disclosed compositionsincludes using the composition as a heat transfer composition in aprocess for producing cooling, wherein the composition is first cooledand stored under pressure and when exposed to a warmer environment, thecomposition absorbs some of the ambient heat, expands, and the warmerenvironment is thusly cooled.

In some embodiments, the compositions as disclosed herein may be usefulin particular in air conditioning applications including but not limitedto chillers, high temperature heat pumps, residential, commercial orindustrial air conditioning systems (including residential heat pumps),and including window, ductless, ducted, packaged terminal, chillers, andthose exterior but connected to the building such as rooftop systems.

In some embodiments, the compositions as disclosed herein may be usefulin particular in refrigeration applications including high, medium orlow temperature refrigeration. High temperature refrigeration systemsinclude those for supermarket produce sections among others. Mediumtemperature refrigeration systems includes supermarket and conveniencestore refrigerated cases for beverages, dairy and other items requiringrefrigeration. Low temperature refrigeration systems include supermarketand convenience store freezer cabinets and displays, ice machines andfrozen food transport. Other specific uses such as in commercial,industrial or residential refrigerators and freezers, ice machines,self-contained coolers and freezers, supermarket rack and distributedsystems, flooded evaporator chillers, direct expansion chillers, walk-inand reach-in coolers and freezers, and combination systems.

In one embodiment, a method is provided for replacing existingrefrigerants, in a system designed to use said existing refrigerants,respectively, wherein said method comprises providing a composition asdisclosed herein. The method may be used, wherein said existingrefrigerants are selected from the group consisting of R-22, R-404A,R-407C, and R-134a.

In another embodiment, the compositions as disclosed herein may be usedas replacements for refrigerants selected from the group consisting ofR-22, R-404A, R-407C, and R-134a. In one embodiment, the compositions asdisclosed herein may be used as replacements for R-22. The replacementmay be made in a system designed to use R-22. In another embodiment, thecompositions as disclosed herein may be used as replacements for R-407C.The replacement may be made in a system designed to use R-407C. Inanother embodiment, the compositions as disclosed herein may be used asreplacements for R-404A. The replacement may be made in a systemdesigned to use R-404A. In another embodiment, the compositions asdisclosed herein may be used as replacements for R-134a. The replacementmay be made in a system designed to use R-134a.

In one embodiment, compositions within about +/−10% of the coolingcapacity of R-134a, R-22 or R-407C are of particular usefulness, as theymay be direct drop-in replacements.

Of note are compositions comprising from about 75 to about 85 weightpercent HFO-1234yf, about 10 weight percent HFC-32, and from about 5 toabout 15 weight percent HFC-152a that provide low GWP replacements forR-134a with improved cooling performance.

Also of utility are compositions comprising from about 58 to about 74weight percent HFO-1234yf; about 21.5 weight percent HFC-32; and fromabout 5 to about 20 weight percent HFC-152a, HFO-1243zf, or mixturesthereof; which provide low GWP replacements for R-22. Also, compositionscomprising from about 58 to about 74 weight percent HFO-1234yf, about21.5 weight percent HFC-32, and from about 5 to about 20 weight percentHFC-152a, HFO-1243zf, or mixtures thereof; provide low GWP replacementsfor R-407C.

Of significant utility, are compositions comprising from about 56 toabout 98 weight percent HFO-1234yf or HFO-1234ze or a mixture thereof;from about 1 to about 43 weight percent HFC-32; and from about 1 toabout 18 weight percent HFC-152a, HFO-1243zf, or mixtures thereof. Ofnote are compositions comprising from about 75 to about 85 weightpercent HFO-1234yf, about 10 weight percent HFC-32, and from about 5 toabout 15 weight percent HFC-152a, HFO-1243zf, or mixtures thereof; whichprovide low GWP replacements for R-134a.

Also of significant utility, are compositions comprising from about 56to about 98 weight percent HFO-1234yf or HFO-1234ze or a mixturethereof;

from about 1 to about 43 weight percent HFC-32; and from about 1 toabout 15 weight percent HFC-152a, HFO-1243zf, or mixtures thereof.

Also of utility are compositions comprising from about 58 to about 74weight percent HFO-1234yf; about 21.5 weight percent HFC-32; and fromabout 5 to about 20 weight percent HFC-152a, HFO-1243zf, or mixturesthereof, which provide low GWP replacements for R-22. Also, compositionscomprising from about 58 to about 74 weight percent HFO-1234yf; about21.5 weight percent HFC-32; and from about 5 to about 20 weight percentHFC-152a, HFO-1243zf, or mixtures thereof; provide low GWP replacementsfor R-407C.

Also of utility are compositions comprising from about 56 weight percentto about 72 weight percent HFO-1234yf; from about 8 weight percent toabout 39 weight percent HFC-32; and from about 5 weight percent to about20 weight percent HFC-152a, that provide low GWP replacements for R-22.Also compositions comprising from about 56 weight percent to about 72weight percent HFO-1234yf; from about 8 weight percent to about 39weight percent HFC-32; and from about 5 weight percent to about 20weight percent HFC-152a, that provide low GWP replacements for R-407C.

Also of particular utility are compositions comprising from about 56weight percent to about 62 weight percent HFO-1234yf; from about 8weight percent to about 29 weight percent HFC-32; from about 5 weightpercent to about 20 weight percent HFC-152a; and about 10 weight percentHFC-134a, that provide low GWP replacements for R-22. Also compositionscomprising from about 56 weight percent to about 62 weight percentHFO-1234yf; from about 8 weight percent to about 29 weight percentHFC-32; from about 5 weight percent to about 20 weight percent HFC-152a;and about 10 weight percent HFC-134a, that provide low GWP replacementsfor R-407C.

In another embodiment, a composition comprising from about 44 to about59 weight percent HFO-1234yf; about 36 weight percent HFC-32; and fromabout 5 to about 20 weight percent HFC-152a, HFO-1243zf, or mixturesthereof; which provide low GWP replacements for R-404A.

In another embodiment, compositions comprising from about 37 to about 53weight percent HFO-1234yf; about 42.5 weight percent HFC-32;

and from about 5 to about 20 weight percent HFC-152a, HFO-1243zf, ormixtures thereof; which provide low GWP replacements for R-404A.

In another embodiment, compositions comprising from about 22 to about 38weight percent HFO-1234yf; about 57.5 weight percent HFC-32; and fromabout 5 to about 20 weight percent HFC-152a, HFO-1243zf, or mixturesthereof, which provide low GWP replacements for R-404A.

Of particular utility,are compositions comprising from about 56 to about98 weight percent trans-HFO-1234ze; from about 1 to about 43 weightpercent HFC-32; and from about 1 to about 20 weight percent HFC-152a,HFO-1243zf, or mixtures thereof;.

Also of note are compositions comprising from about 75 to about 85weight percent trans-HFO-1234ze; about 10 weight percent HFC-32; andfrom about 5 to about 15 weight percent HFC-152a, HFO-1243zf, ormixtures thereof; which provide low GWP replacements for R-134a withimproved cooling performance.

In another embodiment, compositions comprising from about 37 to about 53weight percent trans-HFO-1234ze; about 42.5 weight percent HFC-32; andfrom about 5 to about 20 weight percent HFC-152a, HFO-1243zf, ormixtures thereof; which provide low GWP replacements for R-404A.

In another embodiment, compositions comprising from about 22 to about 38weight percent trans-HFO-1234ze; about 57.5 weight percent HFC-32; andfrom about 5 to about 20 weight percent HFC-152a, HFO-1243zf, ormixtures thereof.

In one embodiment, a method is provided for replacing R-22, R-404A,R-407C, or R-134a, in a system designed to use R-22, R-404A, R-407C, orR-134a, respectively, wherein said method comprises providing acomposition as disclosed herein to said system.

Additionally, in some embodiments, the disclosed compositions mayfunction as primary refrigerants in secondary loop systems that providecooling to remote locations by use of a secondary heat transfer fluid,which may comprise water, a glycol or carbon dioxide.

In another embodiment is provided a method for recharging a heattransfer system that contains a refrigerant to be replaced and alubricant, said method comprising removing the refrigerant to bereplaced from the heat transfer system while retaining a substantialportion of the lubricant in said system and introducing one of thecompositions herein disclosed to the heat transfer system.

In another embodiment, a heat exchange system comprising a compositiondisclosed herein is provided, wherein said system is selected from thegroup consisting of air conditioners, freezers, refrigerators, waterchillers, flooded evaporator chillers, direct expansion chillers,walk-in coolers, heat pumps, mobile refrigerators, mobile airconditioning units, and systems having combinations thereof.

Vapor-compression refrigeration, air-conditioning, or heat pump systemsinclude an evaporator, a compressor, a condenser, and an expansiondevice. A vapor-compression cycle re-uses refrigerant in multiple stepsproducing a cooling effect in one step and a heating effect in adifferent step. The cycle can be described simply as follows. Liquidrefrigerant enters an evaporator through an expansion device, and theliquid refrigerant boils in the evaporator, by withdrawing heat from theenvironment, at a low temperature to form a gas and produce cooling. Thelow-pressure gas enters a compressor where the gas is compressed toraise its pressure and temperature. The higher-pressure (compressed)gaseous refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

In one embodiment, there is provided a heat transfer system containing acomposition as disclosed herein. In another embodiment is disclosed arefrigeration, air-conditioning, or heat pump apparatus containing acomposition as disclosed herein. In another embodiment, is disclosed astationary refrigeration, air-conditioning, or heat pump apparatuscontaining a composition as disclosed herein. In a particularembodiment, is disclosed a medium temperature refrigeration apparatuscontaining the composition of the present invention. In anotherparticular embodiment, is disclosed a low temperature refrigerationapparatus containing the composition of the present invention.

In yet another embodiment is disclosed a mobile refrigeration or airconditioning apparatus containing a composition as disclosed herein.

The compositions as disclosed herein may also be useful as power cycleworking fluids in heat recovery processes, such as organic Rankinecycles. In relation to this embodiment is disclosed a process forrecovering heat which comprises: (a) passing a working fluid through afirst heat exchanger in communication with a process which producesheat; (b) removing said working fluid from said first heat exchanger;(c) passing said working fluid to a device that produces mechanicalenergy; and (d) passing said working fluid to a second heat exchanger.

The power cycle working fluids for the above described method may be anyof the compositions as disclosed herein. In the first heat exchangerheat is absorbed by the working fluid causing it to be evaporated. Theheat source may comprise any source of available heat including wasteheat. Such heat sources include fuel cells, internal combustion engines(exhaust gas), internal compression engines, external combustionengines, operations at oil refineries, petrochemical plants, oil and gaspipelines, chemical industry, commercial buildings, hotels, shoppingmalls supermarkets, bakeries, food processing industries, restaurants,paint curing ovens, furniture making, plastics molders, cement kilns,lumber kilns (drying), calcining operations, steel industry, glassindustry, foundries, smelting, air conditioning, refrigeration, andcentral heating.

The device for producing mechanical energy may be an expander or aturbine thus producing shaft power that can do any kind of mechanicalwork by employing conventional arrangements of belts, pulleys, gears,transmissions or similar devices depending on the desired speed andtorque required. The shaft can be connected to an electricpower-generating device such as an induction generator. The electricityproduced can be used locally or delivered to the grid.

At the second heat exchanger, the working fluid is condensed and thenreturned to the first heat exchanger thus completing the cycle. Acompressor or pump may be included in the cycle between the second heatexchanger and the first heat exchanger to elevate the pressure of theworking fluid.

EXAMPLES

The concepts disclosed herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1 Cooling Performance

Cooling performance for a composition containing HFO-1234yf, HFC-32,HFC-152a, and optionally at least one saturated HFC is determined anddisplayed in Table 1 as compared to R-134a; R-22; R-407C; and R-404A.The pressures, discharge temperatures, COP (energy efficiency) andcooling capacity (cap) are calculated from physical propertymeasurements for the following specific conditions (as typical for airconditioning):

Evaporator temperature −10° C. Condenser temperature   40° C. Subcoolamount    6° K Return gas temperature   18° C. Compressor efficiency 70%Note that the superheat is included in cooling capacity.

TABLE 1 Ratio COP wt % wt % Wt % 1234yf/ Cap Cap rel Rel to Disch DischR32 R1234yf R152a 152a (kJ/m³) to R-22 COP R-22 T (° C.) P (kPa) GWPR-22 2394 100%  2.959 100%  116.8 1532 R-407C 2368 99% 2.917 99% 101.61627 R-134a 1497 63% 3.063 104%  89.8 1017 1430 39 56 5 11.2 2724 114% 2.852 96% 103.9 1865 272 37 58 5 11.6 2674 112%  2.858 97% 102.7 1832258 35 60 5 12.0 2622 110%  2.864 97% 101.5 1799 245 33 62 5 12.4 2570107%  2.871 97% 100.3 1764 231 31 64 5 12.8 2517 105%  2.878 97% 99.01729 218 29 66 5 13.2 2462 103%  2.885 97% 97.8 1693 205 27 68 5 13.62406 101%  2.893 98% 96.6 1655 191 25 70 5 14.0 2349 98% 2.901 98% 95.41617 178 23 72 5 14.4 2291 96% 2.909 98% 94.1 1577 164 34 56 10 5.6 2566107%  2.880 97% 102.2 1751 244 32 58 10 5.8 2516 105%  2.887 98% 101.01717 231 30 60 10 6.0 2464 103%  2.894 98% 99.8 1683 217 28 62 10 6.22411 101%  2.901 98% 98.5 1648 204 26 64 10 6.4 2357 98% 2.909 98% 97.31613 190 24 66 10 6.6 2302 96% 2.917 99% 96.1 1575 177 22 68 10 6.8 224594% 2.929 99% 94.7 1537 164 20 70 10 7.0 2187 91% 2.937 99% 93.5 1497150 18 72 10 7.2 2128 89% 2.946 100%  92.2 1457 137 29 56 15 3.7 2410101%  2.909 98% 100.5 1639 217 27 58 15 3.9 2359 99% 2.916 99% 99.3 1605203 25 60 15 4.0 2306 96% 2.923 99% 98.1 1570 190 23 62 15 4.1 2253 94%2.931 99% 96.8 1534 176 21 64 15 4.3 2198 92% 2.943 99% 95.5 1497 163 1966 15 4.4 2142 89% 2.951 100%  94.2 1459 149 17 68 15 4.5 2084 87% 2.960100%  92.9 1419 136 15 70 15 4.7 2025 85% 2.968 100%  91.6 1379 123 1372 15 4.8 1965 82% 2.977 101%  90.3 1337 109 24 56 20 2.8 2256 94% 2.93799% 98.8 1528 189 22 58 20 2.9 2204 92% 2.944 99% 97.6 1494 176 20 60 203.0 2150 90% 2.956 100%  96.2 1458 162 18 62 20 3.1 2096 88% 2.964 100% 94.9 1421 149 16 64 20 3.2 2040 85% 2.972 100%  93.7 1383 135 14 66 203.3 1982 83% 2.981 101%  92.4 1343 122 12 68 20 3.4 1924 80% 2.990 101% 91.0 1303 109 10 70 20 3.5 1863 78% 2.999 101%  89.7 1261 95 8 72 20 3.61802 75% 3.008 102%  88.3 1218 82 wt % R-134a 10 29 56 5 11.2 2445 102% 2.897 98% 99.1 1673 347 10 22 58 10 5.8 2231 93% 2.934 99% 96.1 1522 30610 15 60 15 4.0 2016 84% 2.975 101%  92.9 1369 265 10 8 62 20 3.1 179775% 3.012 102%  89.5 1213 224

These data indicate that certain compositions of the present inventionwould serve as good replacements for existing refrigerants such asR-134a, R-22, and R-407C. Of note are compositions comprising 56-72%HFO-1234yf, 8-39% HFC-32, and 5-20% HFC-152a that exhibit coolingcapacity that is 75-114% of the cooling capacity of R-22 and R-407C,energy efficiency that is up to 96-102% of the energy efficiency ofR-22, and lower discharge temperatures (thus increasing compressorlife). In another example, compositions comprising 56-62% HFO-1234yf,8-29% HFC-32, and 5-20% HFC-152a, and 10% R-134a exhibit coolingcapacity that is 75-102% of the cooling capacity of R-22 and R-407C and98-102% of the energy efficiency. These compositions also exhibit lowercompressor discharge temperatures. Most preferred are compositionswithin about +/−10% of the cooling capacity of R-22 and R-407C as theymay be direct drop-in replacements.

Example 2 Cooling Performance

Cooling performance for a composition containing HFO-1234yf ortrans-HFO-1234ze, HFC-32, and HFC-152a is determined and displayed inTable 2 as compared to R-134a; R-22; R-407C; and R-404A. The pressures,discharge temperatures, COP (energy efficiency) and cooling capacity(cap) are calculated from physical property measurements for thefollowing specific conditions (as typical for air conditioning):

Evaporator temperature −10° C. Condenser temperature   40° C. Subcoolamount    6° K Return gas temperature   18° C. Compressor efficiency 70%Note that the superheat is included in cooling capacity.

TABLE 2 32/1234/152a HFO/152a Cap Cap COP Rel Disch Disch (wt %) ratio(kJ/m³) rel to: COP to: T (° C.) P (kPa) GWP 134a 134a R-134a 1497 100%3.063 100% 89.8 1017 1430 32/1234yf 10/90 1876 125% 2.966  97% 84.3 129771 32/1234yf/152a 10/85/5 17.0 1878 125% 2.975  97% 85.6 1290 7732/1234yf/152a 10/80/10 8.0 1876 125% 2.984  97% 87.0 1282 8332/1234yf/152a 10/75/15 5.0 1871 125% 2.992  97% 88.3 1272 8932/1234yf/152a 10/30/60 0.5 1740 116% 3.041  99% 100.9 1151 14332/1234yf/152a 10/20/70 0.3 1702 114% 3.049 100% 103.6 1151 15532/t-1234ze 10/90 1494 100% 3.026  99% 93.0 1038 73 32/t-1234ze/152a10/85/5 17.0 1511 101% 3.030  99% 94.0 1044 79 32/t-1234ze/152a 10/80/108.0 1526 102% 3.034  99% 95.0 1049 85 32/t-1234ze/152a 10/75/15 5.0 1540103% 3.037  99% 95.9 1052 91 32/1234ze/152a 10/30/60 0.5 1611 108% 3.058100% 104.0 1067 144 32/1234ze/152a 10/20/70 0.3 1619 108% 3.061 100%105.7 1067 156 R-22 R-22 R-22 2394 100% 2.959 100% 116.8 1532 1810R-407C 2368  99% 2.917  99% 101.6 1627 1774 32/1234yf 21.5/78.5 2259 94% 2.907  98% 91.8 1566 148 32/1234yf/152a 21.5/73.5/5 14.7 2246  94%2.92  99% 93.1 1547 154 32/1234yf/152a 21.5/68.5/10 6.9 2230  93% 2.931 99% 94.4 1527 160 32/1234yf/152a 21.5/63.5/15 4.2 2212  92% 2.941  99%95.8 1506 166 32/1234yf/152a 21.5/58.5/20 2.9 2190  91% 2.946 100% 97.21485 172 404A 404A 404A 2602 100% 2.836 100% 84.9 1833 3922 32/1234yf36/64 2678 103% 2.846 100% 100.8 1848 246 32/1234yf/152a 36/59/5 11.92648 102% 2.861 101% 102.1 1816 252 32/1234yf/152a 36/54/10 5.4 2616101% 2.874 101% 103.4 1783 258 32/1234yf/152a 36/49/15 3.3 2580  99%2.885 102% 104.8 1750 264 32/1234yf/152a 36/44/20 2.2 2543  98% 2.895102% 106.3 1718 270 32/1234yf 42.5/57.5 2846 109% 2.827 100% 105.7 1957289 32/1234yf/152a 42.5/52.5/5 10.5 2809 108% 2.842 100% 106.0 1919 29532/1234yf/152a 42.5/47.5/10 4.8 2769 106% 2.855 101% 107.4 1882 30132/1234yf/152a 42.5/42.5/15 2.8 2726 105% 2.867 101% 108.9 1844 30732/1234yf/152a 42.5/37.5/20 1.9 2681 103% 2.876 101% 110.3 1807 31332/t-1234ze 42.5/57.5 2485  96% 2.857 101% 112.4 1715 29032/t-1234ze/152a 42.5/52.5/5 10.5 2478  95% 2.867 101% 113.2 1701 29632/t-1234ze/152a 42.5/47.5/10 4.8 2469  95% 2.876 101% 113.9 1686 30232/t-1234ze/152a 42.5/42.5/15 2.8 2461  95% 2.884 102% 114.7 1672 30832/t-1234ze/152a 42.5/37.5/20 1.9 2450  94% 2.892 102% 115.5 1658 31432/1234yf 57.5/42.5 3200 123% 2.802  99% 113.7 2170 390 32/1234yf/152a57.5/37.5/5 7.5 3143 121% 2.815  99% 115.2 2122 396 32/1234yf/152a57.5/32.5/10 3.3 3083 118% 2.825 100% 116.8 2074 402 32/1234yf/152a57.5/27.5/15 1.8 3021 116% 2.834 100% 118.3 2027 408 32/1234yf/152a57.5/22.5/20 1.1 2961 114% 2.841 100% 119.9 1982 414 32/t-1234ze57.5/42.5 2878 111% 2.806  99% 120.6 1970 391 32/t-1234ze/152a57.5/37.5/5 8.5 2861 110% 2.818  99% 121.2 1948 397 32/t-1234ze/152a57.5/32.5/10 3.3 2843 109% 2.829 100% 121.9 1926 402 32/t-1234ze/152a57.5/27.5/15 1.8 2823 108% 2.838 100% 122.6 1904 408 32/t-1234ze/152a57.5/22.5/20 1.1 2803 108% 2.846 100% 123.3 1883 414

These data indicate that certain compositions of the present inventionwould serve as good replacements for existing refrigerants such asR-134a, R-22, R-407C, and R-404A. Of note are compositions comprising75-85% HFO-1234yf, 10% HFC-32, and 5-15% HFC-152a that exhibit coolingcapacity that is 125% of the cooling capacity of R-134a, energyefficiency that is up to 6% higher than R-134a, and lower dischargetemperatures (thus increasing compressor life). In another example,compositions comprising 75-85% trans-HFO-1234ze (designated in the tableas t-1234ze), 10% HFC-32, and 5-15% HFC-152a exhibit cooling capacitythat is equivalent to the cooling capacity of R-134a and 7% higherenergy efficiency. In another example, compositions comprising about58-74% HFO-1234yf, about 21.5% HFC-32, and 5-20% HFC-152a exhibitcooling capacity that is from 90-95% of the cooling capacity of R-22 andR-407C, 3-4% better energy efficiency and lower discharge temperatures.Similarly, a composition comprising 44-59% HFO-1234yf, 36% HFC-32 and5-20% HFC-152a exhibits energy efficiency and cooling capacity that isequivalent to the cooling capacity of R-404A. In another example,compositions comprising about 37-53% HFO-1234yf, about 42.5% HFC-32, and5-20% HFC-152a exhibit cooling capacity 103-108% of the cooling capacityof R-404A, and equivalent energy efficiency. In another example,compositions comprising about 37-53% trans-HFO-1234ze, about 42.5%HFC-32, and 5-20% HFC-152a exhibit cooling capacity within 6% of thecooling capacity of R-404A, and equivalent energy efficiency. In anotherexample, composition comprising 22-38% HFO-1234yf, 57.5% HFC-32 and5-20% HFC-152a exhibits a cooling capacity that is 114-121% of thecooling capacity of R-404A and equivalent energy efficiency. In anotherexample, composition comprising 22-38% trans-HFO-1234ze, 57.5% HFC-32and 5-20% HFC-152a exhibits a cooling capacity that is 108-110% of thecooling capacity of R-404A and equivalent energy efficiency.

Example 3

The burning velocity for compositions of the present invention wasdetermined relative to R-32 by measuring the pressure rise in a 12-litervessel. The burning velocity of HFC-32 is 6.7 cm/s (ISO-817).Compositions were introduced at stoichiometric amounts in air into the12-liter vessel at 25° C. and atmospheric pressure. The compositionswere ignited using a fused-Nichrome wire-igniter and the time to reach apressure of 2 atmosphere was measured. The ratio of the time for eachcomposition relative to the time for R-32 to reach 2 atm was reported.This value was then used to estimate a burning velocity for each mixtureassuming that R-32 burning velocity is 6.7 cm/s. Results are shown inTable 1 below:

TABLE 3 Ratio Ratio wt % of time Estimated HFO- 1234yf/ Time to 2Burning R-152a 1234yf R-32 wt % to 2 atm vs Velocity (wt %) (wt %) (wt%) 152a atm (s) R-32 (cm/s) 0.0 0.0 100.0 #N/A 0.297 1.000 6.7 20.0 22.557.5 1.1 0.150 1.983 13.3 20.0 44.0 36.0 2.2 0.153 1.944 13.0 20.0 37.542.5 1.9 0.157 1.894 12.7 20.0 58.5 21.5 2.9 0.200 1.487 10.0 15.0 27.557.5 1.8 0.220 1.355 9.1 15.0 42.5 42.5 2.8 0.224 1.328 8.9 10.0 47.542.5 4.8 0.315 0.946 6.3 15.0 49.0 36.0 3.3 0.342 0.870 5.8 10.0 32.557.5 3.3 0.352 0.845 5.7 15.0 63.5 21.5 4.2 0.394 0.755 5.1 10.0 54.036.0 5.4 0.406 0.733 4.9 10.0 68.5 21.5 6.9 0.562 0.530 3.5

TABLE 3.1 Ratio wt % Ratio of Estimated 1234yf/ Time time to 2 BurningR-152a HFO R-32 wt % to 2 atm vs Velocity (wt %) (wt %) (wt %) 152a atm(s) R-32 (cm/s) 20.0 37.5 42.5 1.9 0.157 1.894 12.7 See (1234yf) Example3 20.0 37.5 (trans- 42.5 1.9 0.152 1.957 13.1 HFO-1234ze)

Results show up to about 15 wt % HFC-152a can be added to R32/HFO-1234yfand/or R32/trans-HFO-1234ze compositions and maintain a burning velocitybelow about 10 cm/s which would be considered 2L flammability by ASHRAEStd 34. Alternatively, the ratio of wt % of HFO-1234yf to HFC-152a inthe composition was plotted versus the estimated burning velocity inFIG. 1. The graph shows the 32/152a/1234yf mixtures will have burningvelocity below about 10 cm/s if the ratio of HFO-1234yf/HFC-152 is atleast about 2.8.

Example 4 Global Warming Potentials

Values for global warming potential (GWP) for some of the disclosedcompositions are listed in Table 4 as compared to GWP values forexisting refrigerants such as R-22, HFC-134a, R-404A, and R-407C. TheGWP for the pure components are listed for reference. The GWP values forcompositions containing more than one component are calculated asweighted averages of the individual component GWP values. The values forthe HFCs are taken from the “Climate Change 2007—IPCC (IntergovernmentalPanel on Climate Change) Fourth Assessment Report on Climate Change”,from the section entitled “Working Group 1 Report: “The Physical ScienceBasis”, Chapter 2, pp. 212-213, Table 2.14. The value for HFO-1234yf waspublished in Papadimitriou et al., Physical Chemistry Chemical Physics,2007, vol. 9, pp. 1-13. Specifically, the 100 year time horizon GWPvalues are used. The value for trans-HFO-1234ze was presented by Higashiat the 2010 International Symposium on Next-generation Air Conditioningand Refrigeration Technology, Feb. 17-19, 2010, Tokyo, Japan.

TABLE 4 Component or Composition GWP R-22 1810 HFC-134a 1430 R-404A 3922R-407C 3985 HFC-32 675 HFC-152a 124 HFO-1234yf 4 trans-HFO-1234ze 6HFO-1234yf/HFC-32/HFC-152a (85/10/5 wt %) 77 HFO-1234yf/HFC-32/HFC-152a(80/10/10 wt %) 83 HFO-1234yf/HFC-32/HFC-152a (75/10/15 wt %) 89trans-HFO-1234ze/HFC-32/HFC-152a (85/10/5 wt %) 79trans-HFO-1234ze/HFC-32/HFC-152a (80/10/10 wt %) 85trans-HFO-1234ze/HFC-32/HFC-152a (75/10/15 wt %) 91HFO-1234yf/HFC-32/HFC-152a (73.5/21.5/5 wt %) 154HFO-1234yf/HFC-32/HFC-152a (68.5/21.5/10 wt %) 160HFO-1234yf/HFC-32/HFC-152a (63.5/21.5/15 wt %) 166trans-HFO-1234ze/HFC-32/HFC-152a (73.55/21.5/5 wt %) 156trans-HFO-1234ze/HFC-32/HFC-152a (68.5/21.5/10 wt %) 162trans-HFO-1234ze/HFC-32/HFC-152a (63.5/21.5/15 wt %) 168HFO-1234yf/HFC-32/HFC-152a (59/36/5 wt %) 252trans-HFO-1234ze/HFC-32/HFC-152a (59/36/5 wt %) 253HFO-1234yf/HFC-32/HFC-152a (37.5/57.5/5 wt %) 396HFO-1234yf/HFC-32/HFC-152a (32.5/57.5/10 wt %) 402HFO-1234yf/HFC-32/HFC-152a (27.5/57.5/15wt %) 408trans-HFO-1234ze/HFC-32/HFC-152a (37.5/57.5/5 wt %) 396trans-HFO-1234ze/HFC-32/HFC-152a (32.5/57.5/10 wt %) 402trans-HFO-1234ze/HFC-32/HFC-152a (27.5/57.5/15wt %) 408

Many compositions as disclosed herein provide significantly lower GWPalternatives to existing refrigerants such as R-22, R-404A, R-407C, andHFC-134a. Also, many of the compositions of the present inventionprovide lower GWP than pure HFC-32 while some provide lower GWP thaneven pure HFC-152a.

Example 5 Cooling Performance

Cooling performance for a composition containing HFO-1234yf, HFC-32,HFC-152 and/or HFO-1243zf, and optionally at least one saturated HFC isdetermined and displayed in Table 5 as compared to R-134a; R-22; R-407C;and R-404A. The pressures, discharge temperatures, COP (energyefficiency) and cooling capacity (cap) are calculated from physicalproperty measurements for the following specific conditions (as typicalfor air conditioning):

Evaporator temperature −10° C. Condenser temperature   40° C. Subcoolamount    6° K Return gas temperature   18° C. Compressor efficiency 70%Note that the superheat is included in cooling capacity.

Ratio 1234yf/ Cap COP Disch wt % wt % Wt % Wt % (152a + Cap rel to Relto Disch P R32 R1234yf R152a 1243zf 1243zf) (kJ/m³) R-22 COP R-22 T (C.)(kPa) GWP R-22 2394 100%  2.959 100%  116.8 1532 1810 R-407C 2368 99%2.917 99% 101.6 1627 1774 R-134a 1497 63% 3.063 104%  89.8 1017 1430 3956 0 5 11.2 2714 113%  2.846 96% 103.2 1865 266 37 58 2.5 2.5 11.6 2669111%  2.855 96% 102.3 1832 255 31 64 0 5 12.8 2504 105%  2.872 97% 98.31727 212 29 66 2.5 2.5 13.2 2456 103%  2.883 97% 97.4 1692 202 25 70 0 514.0 2334 97% 2.895 98% 94.6 1613 172 23 72 2.5 2.5 14.4 2283 95% 2.91198% 93.7 1575 161 34 56 0 10 5.6 2547 106%  2.870 97% 100.7 1750 232 3258 5 5 5.8 2506 105%  2.882 97% 100.2 1717 225 26 64 0 10 6.4 2332 97%2.899 98% 95.7 1607 179 24 66 5 5 6.6 2289 96% 2.912 98% 95.3 1572 17120 70 0 10 7.0 2157 90% 2.927 99% 91.9 1488 138 18 72 5 5 7.2 2113 88%2.941 99% 91.4 1452 131 29 56 0 15 3.7 2383 100%  2.895 98% 98.2 1635199 27 58 7.5 7.5 3.9 2346 98% 2.909 98% 98.1 1603 194 21 64 0 15 4.32160 90% 2.929 99% 93.0 1486 145 19 66 7.5 7.5 4.4 2123 89% 2.944 99%93.0 1453 141 15 70 0 15 4.7 1980 83% 2.954 100%  89.1 1362 105 13 727.5 7.5 4.8 1942 81% 2.971 100%  89.1 1328 100 24 56 0 20 2.8 2218 93%2.919 99% 95.5 1521 165 20 60 20 3.0 2131 89% 2.948 100%  94.6 1453 16218 62 0 20 3.1 2047 86% 2.946 100%  91.6 1406 125 16 64 10 10 3.2 201784% 2.964 100%  92.0 1375 123 14 66 0 20 3.3 1927 80% 2.964 100%  88.91323 98 12 68 10 10 3.4 1897 79% 2.982 101%  89.3 1292 97 wt % R-134a 1029 56 0 5 11.2 2436 102%  2.892 98% 98.3 1672 341 10 22 58 5 5 5.8 222293% 2.933 99% 95.1 1520 300 10 15 60 0 15 4.0 1981 83% 2.962 100%  90.21358 247 10 8 62 10 10 3.1 1774 74% 3.006 102%  87.6 1203 212

These data indicate that certain compositions of the present inventionwould serve as good replacements for existing refrigerants such asR-134a, R-22, and R-407C. Of note are compositions comprising 56-72%HFO-1234yf, 12-39% HFC-32, and 0-20% HFC-152a and 0-20% HFO-1243zf thatexhibit cooling capacity that is 79-113% of the cooling capacity of R-22and R-407C, energy efficiency that is up to 96-101% of the energyefficiency of R-22 and R-407C, and lower discharge temperatures (thusincreasing compressor life). In another example, compositions comprising56-62% HFO-1234yf, 8-29% HFC-32, and 0-10% HFC-152a, 0-15% HFO-1243zf,and 10% R-134a exhibit cooling capacity that is 74-102% of the coolingcapacity of R-22 and R-407C and 98-102% of the energy efficiency. Thesecompositions also exhibit lower compressor discharge temperatures. Mostpreferred are compositions within about +/−10% of the cooling capacityof R-22 and R-407C as they may be direct drop-in replacements.

Selected Embodiments

-   Embodiment A-I. A composition comprising HFO-1234yf or    trans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a,    HFO-1243zf or mixture thereof; wherein said HFO-1234yf or    trans-HFO-1234ze or a mixture thereof is at least 56 weight percent    of the total weight of said composition.-   Embodiment A-II. A composition comprising HFO-1234yf or    trans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a,    HFO-1243zf or mixture thereof; wherein said HFC-32 is at most 29    weight percent of the total weight of said composition;-   Embodiment A-III. A composition comprising HFO-1234yf or    trans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a,    HFO-1243zf or mixture thereof; wherein said HFC-152a, HFO-1243zf or    mixture thereof is at least 56 weight percent of the total weight of    said composition.-   Embodiment A-IV. A composition comprising HFO-1234yf or    trans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a,    HFO-1243zf or mixture thereof; wherein said HFC-32 is at least 56    weight percent of the total weight of said composition.-   Embodiment A-V. A composition comprising HFO-1234yf or    trans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a,    HFO-1243zf or mixture thereof, wherein said composition comprises    trans-HFO-1234ze; HFC-32; and HFC-152a, HFO-1243zf or mixture    thereof.-   Embodiment A-VI. A composition comprising HFO-1234yf or    trans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a,    HFO-1243zf or mixture thereof; wherein said HFO-1243zf or mixture    thereof with HFC-152a is at most 20 weight percent of the total    weight of said composition.-   Embodiment B-I. The composition as recited in any of Embodiments A-I    to A-VI, wherein said composition has a cooling capacity in the    range of from about 75% to about 130% of at least one existing    refrigerant.-   Embodiment B-II. The composition as recited in any of Embodiments    A-I to A-VI, wherein said composition has a cooling capacity in the    range of from about 80% to about 120% of at least one existing    refrigerant.-   Embodiment B-III. The composition as recited in any of Embodiments    A-I to A-VI, wherein said composition has a cooling capacity in the    range of from about 90% to about 110% of at least one existing    refrigerant.-   Embodiment B-IV. The composition as recited in any of Embodiments    A-I to A-VI or B-I to B-III, wherein said existing refrigerant is    selected from the group consisting of R-22, HFC-134a, R-404A, and    R-407C.-   Embodiment B-V. The composition as recited in any of Embodiments A-I    to A-VIl or B-I to B-IV, wherein the flammability of said    composition is classified at most as 2L.-   Embodiment C-I. The composition as recited in any of Embodiments    A-I, A-II, A-V, A-VI or B-I to B-V, comprising from about 56 to    about 98 weight percent HFO-1234yf or trans-HFO-1234ze or a mixture    thereof; about 1-29 weight percent HFC-32; and from about 1 to about    18 weight percent HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment C-II. The composition as recited in any of Embodiments    A-I, A-II, A-V, A-VI or B-I to B-V, comprising from about 60 to    about 98 weight percent HFO-1234yf or trans-HFO-1234ze or a mixture    thereof; about 5-25 weight percent HFC-32; and from about 5 to about    15 weight percent HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment CAI. The composition as recited in any of Embodiments    A-I, A-II, A-V, A-VI or B-I to B-V, comprising from about 75 to    about 85 weight percent HFO-1234yf or trans-HFO-1234ze or a mixture    thereof; about 10 weight percent HFC-32; and from about 5 to about    15 weight percent HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment C-IV. The composition as recited in any of Embodiments    A-I, A-II, A-V, A-VI or B-I to B-V, comprising from about 58 to    about 73.5 weight percent HFO-1234yf or trans-HFO-1234ze or a    mixture thereof; about 21.5 weight percent HFC-32; and from about 5    to about 20 weight percent HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment C-V. The compositions as recited in any of Embodiments    A-I, A-II, A-V, A-VI or B-I to B-V comprising from about 56 to about    98 weight percent HFO-1234yf or HFO-1234ze or a mixture thereof;    from about 1 to about 43 weight percent HFC-32; and from about 1 to    about 18 weight percent HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment C-VI. The compositions as recited in any of Embodiments    A-I, A-V, A-VI or B-I to B-V comprising from about 56 to about 98    weight percent HFO-1234yf or HFO-1234ze or a mixture thereof; from    about 1 to about 43 weight percent HFC-32; and from about 1 to about    15 weight percent HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment C-VII. The compositions as recited in any of Embodiments    A-I, A-V, A-VI or B-I to B-V comprising from about 56 to about 98    weight percent trans-HFO-1234ze; from about 1 to about 43 weight    percent HFC-32; and from about 1 to about 20 weight percent    HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment C-VIII. The composition as recited in any of Embodiments    A-IV, A-V, A-VI or B-I to B-V, comprising from about 22 to about 38    weight percent HFO-1234yf or trans-HFO-1234ze or a mixture thereof;    about 57.5 weight percent HFC-32; and from about 5 to about 20    weight percent HFC-152a, HFO-1243zf or mixture thereof.-   Embodiment D-I. The composition as recited in any of Embodiments A-I    to A-VI, B-I to B-V or C-I to C-VIII, further comprising at least    one saturated HFC in the range of from greater than 0 weight percent    to about 10 weight percent.-   Embodiment D-II. The composition as recited in Embodiment D-I,    wherein said at least one saturated HFC is HFC-134a.-   Embodiment D-III. The composition as recited in any of Embodiments    A-I to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-II, wherein the    GWP of said composition is less than the GWP of at least one    refrigerant selected from the group consisting of R-134a, R-22,    R-407C, and R-404A.-   Embodiment D-IV. The composition as recited in any of Embodiments    A-I to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-III, wherein the    ratio of said HFO-1234yf, trans-HFO-1234ze or a mixture thereof to    HFC-152a, HFO-1243zf or mixture thereof is in the range of from    about 1:1 to about 20:1.-   Embodiment D-V. The composition as recited in any of Embodiments A-I    to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV, further    comprising at least one lubricant selected from the group consisting    of mineral oils, alkylbenzenes, synthetic paraffins, synthetic    naphthenes, poly alpha olefins, polyalkylene glycols, dibasic acid    esters, polyesters, neopentyl esters, polyvinyl ethers, silicones,    silicate esters, fluorinated compounds, phosphate esters and    mixtures thereof.-   Embodiment D-VI. The composition as recited in any of Embodiments    A-I to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-V, further    comprising at least one additive selected from the group consisting    of lubricants, dyes (including UV dyes), solubilizing agents,    compatibilizers, stabilizers, tracers, perfluoropolyethers,    anti-wear agents, extreme pressure agents, corrosion and oxidation    inhibitors, metal surface energy reducers, metal surface    deactivators, free radical scavengers, foam control agents,    viscosity index improvers, pour point depressants, detergents,    viscosity adjusters, and mixtures thereof.-   Embodiment E-I. A process to produce cooling comprising condensing    the composition of any of Embodiments A-I to A-VI, B-I to B-V, C-I    to C-VIII, or D-I to D-IV and thereafter evaporating said    composition in the vicinity of a body to be cooled.-   Embodiment E-II. A process to produce heat comprising condensing the    composition of any of Embodiments A-I to A-VI, B-I to B-V, C-I to    C-VIII, or D-I to D-IV in the vicinity of a body to be heated and    thereafter evaporating said composition.-   Embodiment E-III. A method for replacing existing refrigerants, in a    system suitable for use with said existing refrigerants,    respectively, wherein said method comprises providing the    composition of any of Embodiments A-I to A-VI, B-I to B-V, C-I to    C-VIII, or D-I to D-IV to said system.-   Embodiment E-IV. A method for replacing existing refrigerants, in a    system designed to use said existing refrigerants, respectively,    wherein said method comprises providing the composition of any of    Embodiments A-I to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV    to said system.-   Embodiment E-V. The method as recited in Embodiment E-IV, wherein    said existing refrigerants are selected from R-22, R-404A, R-407C,    and R-134a.-   Embodiment E-VI. Use of any of Embodiments A-I to A-VI, B-I to    B-III, B-V, or C-I to C-VIII as a replacement for R-22.-   Embodiment E-VII. Use of any of Embodiments A-I to A-VI, B-I to    B-III, B-V, or C-I to C-VIII as a replacement for R407.-   Embodiment E-VIII. Use of any of Embodiments A-I to A-VI, B-I to    B-III, B-V, or C-I to C-VIII as a replacement for R-404A.-   Embodiment E-IX. Use of any of Embodiments A-I to A-VI, B-I to    B-III, B-V, or C-I to C-VIII as a replacement for R-134a.-   Embodiment F-I. A refrigeration, air-conditioning or heat pump    apparatus containing the composition of any of Embodiments A-I to    A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV.-   Embodiment F-II. A stationary air conditioning apparatus containing    the composition of any of Embodiments A-I to A-VI, B-I to B-V, C-I    to C-VIII, or D-I to D-IV.-   Embodiment F-III. A stationary refrigeration system containing the    composition of any of Embodiments A-I to A-VI, B-I to B-V, C-I to    C-VIII, or D-I to D-IV.-   Embodiment F-IV. An automotive air conditioner or heat pump    containing the composition of any of Embodiments A-I to A-VI, B-I to    B-V, C-I to C-VIII, or D-I to D-IV.-   Embodiment F-V. The use of the composition of any of Embodiments A-I    to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a power cycle    working fluid.-   Embodiment F-VI. A process for recovering heat which comprises: (a)    passing a working fluid comprising a composition of any of    Embodiments A-I to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV    through a first heat exchanger in communication with a process which    produces heat; (b) removing said working fluid from said first heat    exchanger; (c) passing said working fluid to a device that produces    mechanical energy; and (d) passing said working fluid to a second    heat exchanger.-   Embodiment F-VII. Use of the composition of any of Embodiments A-I    to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a refrigerant    in a refrigeration, air conditioning or heat pump system.-   Embodiment F-VIII. Use of the composition of any of Embodiments A-I    to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a refrigerant    in a stationary air conditioning system.-   Embodiment F-IX. Use of the composition of any of Embodiments A-I to    A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a refrigerant in    a stationary refrigeration system.-   Embodiment F-X. Use of the composition of any of Embodiments A-I to    A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a refrigerant in    a mobile air conditioning system.-   Embodiment F-XI. Use of the composition of any of Embodiments A-I to    A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a refrigerant in    an automobile air conditioning or heat pump system.-   Embodiment F-XII. Use of the composition of any of Embodiments A-I    to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a refrigerant    in a chiller.-   Embodiment F-XIII. Use of the composition of any of Embodiments A-I    to A-VI, B-I to B-V, C-I to C-VIII, or D-I to D-IV as a refrigerant    in a centrifugal chiller.-   Embodiment G-I. A composition comprising HFO-1234yf or    trans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a,    HFO-1243zf or mixture thereof; wherein the HFC-152a, HFO-1243zf or    mixture thereof is in the range of from about 14 weight percent to    about 16 weight percent, and wherein said composition has a cooling    capacity in the range of from about 75% to about 130% of at least    one refrigerant selected from the group consisting of R-22,    HFC-134a, R-404A, and R-407C.-   Embodiment G-II. The composition as recited in Embodiment G-I,    further comprising at least one lubricant selected from the group    consisting of mineral oils, alkylbenzenes, synthetic paraffins,    synthetic naphthenes, poly alpha olefins, polyalkylene glycols,    dibasic acid esters, polyesters, neopentyl esters, polyvinyl ethers,    silicones, silicate esters, fluorinated compounds, phosphate esters    and mixtures thereof.-   Embodiment G-III. The composition as recited in any of Embodiments    G-I to G-II, further comprising at least one additive selected from    the group consisting of lubricants, dyes (including UV dyes),    solubilizing agents, compatibilizers, stabilizers, tracers,    perfluoropolyethers, anti-wear agents, extreme pressure agents,    corrosion and oxidation inhibitors, metal surface energy reducers,    metal surface deactivators, free radical scavengers, foam control    agents, viscosity index improvers, pour point depressants,    detergents, viscosity adjusters, and mixtures thereof.-   Embodiment G-IV. A process to produce cooling comprising condensing    the composition of Embodiment G-I and thereafter evaporating said    composition in the vicinity of a body to be cooled.-   Embodiment G-V. A process to produce heat comprising condensing the    composition of Embodiment G-I in the vicinity of a body to be heated    and thereafter evaporating said composition.-   Embodiment G-VI. A refrigeration, air-conditioning or heat pump    apparatus containing the composition of any of Embodiments G-I to    G-III.-   Embodiment G-VII. A stationary air conditioning apparatus containing    the composition of any of Embodiments G-I to G-III.-   Embodiment G-VIII. A stationary refrigeration system containing the    composition of any of Embodiments G-I to G-III.-   Embodiment G-IX. An automotive air conditioner or heat pump    containing the composition of any of Embodiments G-I to G-III.-   Embodiment G-X. The use of the composition of any of Embodiments G-I    to G-III as a power cycle working fluid.-   Embodiment G-Xl. A process for recovering heat which comprises: (a)    passing a working fluid comprising a composition of Embodiments G-I    to G-III through a first heat exchanger in communication with a    process which produces heat; (b) removing said working fluid from    said first heat exchanger; (c) passing said working fluid to a    device that produces mechanical energy; and (d) passing said working    fluid to a second heat exchanger.-   Embodiment H-I. A method for replacing R-22, R-404A, R-407C, or    R-134a, in a system designed to use R-22, R-404A, R-407C, or R-134a,    respectively, wherein said method comprises providing the    composition of any of Embodiments A-I to A-VI, B-I to B-V, C-I to    C-VIII, or D-I to D-IV to said system.

What is claimed is:
 1. A composition comprising HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a, HFO-1243zf,or a mixture thereof; wherein said composition is selected from thegroup consisting of: (I) a first composition, wherein said HFO-1234yf ortrans-HFO-1234ze or a mixture thereof is at least 56 weight percent ofthe total weight of said first composition; (II) a second composition,wherein said HFC-32 is at most 29 weight percent of the total weight ofsaid second composition; (III) a third composition, wherein saidHFC-152a is at least 56 weight percent of the total weight of said thirdcomposition; (IV) a fourth composition, wherein said HFC-32 is at least56 weight percent of the total weight of said fourth composition;(V) afifth composition comprising trans-HFO-1234ze; HFC-32; and HFC-152a,HFO-1243zf or mixture thereof; and (VI) a sixth composition, whereinsaid HFO-1243zf or mixture thereof with HFC-152a is at most 20 weightpercent of the total weight of said sixth composition.
 2. Thecomposition as recited in claim 1, wherein said composition has acooling capacity in the range of from about 75% to about 130% of atleast one existing refrigerant.
 3. The composition as recited in claim2, wherein said existing refrigerant is selected from the groupconsisting of R-22, HFC-134a, R-404A, and R-407C.
 4. The composition asrecited in claim 3, wherein the flammability of said composition isclassified at most as 2L.
 5. The composition as recited in claim 1,comprising from about 56 to about 98 weight percent HFO-1234yf ortrans-HFO-1234ze or a mixture thereof, from about 1 to about 29 weightpercent HFC-32, and from about 1 to about 18 weight percent HFC-152a,HFO-1243zf or mixture thereof.
 6. The composition as recited in claim 1,comprising from about 60 to about 98 weight percent HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; from about 5 to about 25 weightpercent HFC-32; and from about 5 to about 15 weight percent HFC-152a,HFO-1243zf or mixture thereof.
 7. The composition as recited claim 1,comprising from about 75 to about 85 weight percent HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; about 10 weight percent HFC-32;and from about 5 to about 15 weight percent HFC-152a, HFO-1243zf ormixture thereof.
 8. The composition as recited in claim 1, comprisingfrom about 58 to about 73.5 weight percent HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; about 21.5 weight percent HFC-32;and from about 5 to about 20 weight percent HFC-152a, HFO-1243zf ormixture thereof.
 9. The composition as recited in claim 1, comprisingfrom about 22 to about 38 weight percent HFO-1234yf or trans-HFO-1234zeor a mixture thereof, about 57.5 weight percent HFC-32 and from about 5to about 20 weight percent HFC-152a, HFO-1243zf or mixture thereof. 10.The composition as recited in claim 1, further comprising at least onesaturated HFC in the range of from greater than 0 weight percent toabout 10 weight percent.
 11. The composition as recited in claim 10,wherein said at least one saturated HFC is HFC-134a.
 12. The compositionas recited in claim 2, wherein the GWP of said composition is less thanthe GWP of at least one refrigerant selected from the group consistingof R-134a, R-22, R-407C, and R-404A.
 13. The composition as recited inclaim 1, wherein the ratio of said HFO-1234yf or trans-HFO-1234ze or amixture thereof to HFC-152a, HFO-1243zf or mixture thereof is in therange of from about 1:1 to about 20:1.
 14. The composition as recited inclaim 1, further comprising at least one lubricant selected from thegroup consisting of mineral oils, alkylbenzenes, synthetic paraffins,synthetic naphthenes, poly alpha olefins, polyalkylene glycols, dibasicacid esters, polyesters, neopentyl esters, polyvinyl ethers, silicones,silicate esters, fluorinated compounds, phosphate esters and mixturesthereof.
 15. The composition as recited in claim 1, further comprisingat least one additive selected from the group consisting of lubricants,dyes (including UV dyes), solubilizing agents, compatibilizers,stabilizers, tracers, perfluoropolyethers, anti-wear agents, extremepressure agents, corrosion and oxidation inhibitors, metal surfaceenergy reducers, metal surface deactivators, free radical scavengers,foam control agents, viscosity index improvers, pour point depressants,detergents, viscosity adjusters, and mixtures thereof.
 16. A process toproduce cooling comprising condensing the composition of claim 1 andthereafter evaporating said composition in the vicinity of a body to becooled.
 17. A process to produce heat comprising condensing thecomposition of claim 1 in the vicinity of a body to be heated andthereafter evaporating said composition.
 18. A method for replacingexisting refrigerants, in a system designed to use said existingrefrigerants, respectively, wherein said method comprises providing thecomposition of claim 1 to said system.
 19. The method as recited inclaim 18, wherein said existing refrigerants are selected from R-22,R-404A, R-407C, and R-134a.
 20. A refrigeration, air-conditioning orheat pump apparatus containing the composition of claim
 1. 21. Astationary air conditioning apparatus containing the composition ofclaim
 1. 22. A stationary refrigeration system containing thecomposition of claim
 1. 23. A process for recovering heat whichcomprises: (a) passing a working fluid comprising a composition of claim1 through a first heat exchanger in communication with a process whichproduces heat; (b) removing said working fluid from said first heatexchanger; (c) passing said working fluid to a device that producesmechanical energy; and (d) passing said working fluid to a second heatexchanger.
 24. An automotive air conditioner or heat pump containing thecomposition of claim
 1. 25. A composition comprising HFO-1234yf ortrans-HFO-1234ze or a mixture thereof; HFC-32; and HFC-152a, HFO-1243zfor mixture thereof; wherein the HFC-152a, HFO-1243zf or mixture thereofis in the range of from about 14 weight percent to about 16 weightpercent, and wherein said composition has a cooling capacity in therange of from about 75% to about 130% of at least one compound selectedfrom the group consisting of R-22, HFC-134a, R-404A, and R-407C.
 26. Thecomposition as recited in claim 25, further comprising at least onelubricant selected from the group consisting of mineral oils,alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly alphaolefins, polyalkylene glycols, dibasic acid esters, polyesters,neopentyl esters, polyvinyl ethers, silicones, silicate esters,fluorinated compounds, phosphate esters and mixtures thereof.
 27. Thecomposition as recited in claim 25, further comprising at least oneadditive selected from the group consisting of lubricants, dyes(including UV dyes), solubilizing agents, compatibilizers, stabilizers,tracers, perfluoropolyethers, anti-wear agents, extreme pressure agents,corrosion and oxidation inhibitors, metal surface energy reducers, metalsurface deactivators, free radical scavengers, foam control agents,viscosity index improvers, pour point depressants, detergents, viscosityadjusters, and mixtures thereof.
 28. A process to produce coolingcomprising condensing the composition of claim 25 and thereafterevaporating said composition in the vicinity of a body to be cooled. 29.A process to produce heat comprising condensing the composition of claim25 in the vicinity of a body to be heated and thereafter evaporatingsaid composition.
 30. A method for replacing R-22, R-404A, R-407C, orR-134a, in a system designed to use R-22, R-404A, R-407C, or R-134a,respectively, wherein said method comprises providing the composition ofclaim 1 to said system.
 31. A refrigeration, air-conditioning or heatpump apparatus containing composition of claim
 25. 32. A stationary airconditioning apparatus containing the composition of claim
 25. 33. Astationary refrigeration system containing the composition of claim 25.34. A process for recovering heat which comprises: (a) passing a workingfluid comprising a composition of claim 25 through a first heatexchanger in communication with a process which produces heat; (b)removing said working fluid from said first heat exchanger; (c) passingsaid working fluid to a device that produces mechanical energy; and (d)passing said working fluid to a second heat exchanger.
 35. An automotiveair conditioner or heat pump containing the composition of claim 25.